CN104673291A - Nitrogen-zirconate luminescent thin film, electroluminescent device and preparation methods of nitrogen-zirconate luminescent thin film and electroluminescent device - Google Patents
Nitrogen-zirconate luminescent thin film, electroluminescent device and preparation methods of nitrogen-zirconate luminescent thin film and electroluminescent device Download PDFInfo
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Abstract
The invention relates to a nitrogen-zirconate luminescent thin film, an electroluminescent device and preparation methods of the nitrogen-zirconate luminescent thin film and the electroluminescent device. The chemical formula of the nitrogen-zirconate luminescent thin film is MeZr2O2N2:xCe<3+>, wherein x ranges from 0.01 to 0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn. The nitrogen-zirconate luminescent thin film prepared by adopting a pulsed laser deposition method has the advantages that MeZr2O2N2 is adopted as a matrix, Ce<3+> is adopted as luminescent ions and is used as a main luminescent center, not only are the luminescent intensity and luminescent efficiency of the luminescent thin film improved and is the structure stability of the luminescent thin film improved, but also the complexity of the preparation method is reduced, the production efficiency is improved and more suitability for industrial application is achieved.
Description
Technical field
The present invention relates to photoelectric semiconductor material technical field, particularly relate to a kind of nitrogen zirconate light-emitting film, electroluminescent device and the preparation method of the two.
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.Compared with traditional electroluminescent device, light-emitting film contrast gradient, thermal conduction, homogeneity, with the tack, outgas speed etc. of substrate in all demonstrate stronger superiority, therefore prepare light-emitting film of good performance and there is very great meaning.
Nitrogen zirconate light-emitting film is the popular research material of electroluminescent device, still constantly improving in research and development at present, but preparing this type of light-emitting film also exists that technique is more complicated, equipment costly, and the problem such as the luminous intensity of the nitrogen zirconate light-emitting film of preparation is not high.
Summary of the invention
The object of the present invention is to provide a kind of nitrogen zirconate light-emitting film, not high for the luminous intensity solving nitrogen zirconate light-emitting film in prior art, preparation technology is more complicated and Preparation equipment problem costly.
The present invention also aims to the preparation method that a kind of nitrogen zirconate light-emitting film is provided, for the preparation of above-mentioned nitrogen zirconate light-emitting film.
The present invention also aims to provide a kind of electroluminescent device, comprise the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, wherein the material of luminescent layer is above-mentioned nitrogen zirconate light-emitting film.
The present invention also aims to the preparation method that a kind of electroluminescent device is provided, for the preparation of above-mentioned electroluminescent device.
For reaching above-mentioned purpose, the technical solution adopted in the present invention is:
A kind of nitrogen zirconate light-emitting film of the present invention, the chemical formula of described nitrogen zirconate light-emitting film is MeZr
2o
2n
2: xCe
3+; Wherein,
MeZr
2o
2n
2for matrix, Ce
3+for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one.
In one embodiment of this invention, x is 0.03.
In one embodiment of this invention, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
The preparation method of a kind of nitrogen zirconate light-emitting film of the present invention, comprises the following steps:
A () takes MeO, ZrO that mol ratio is 1:0.5:0.5:x
2, Zr
3n
4and CeO
2powder, after Homogeneous phase mixing, is that under the condition of 900 DEG C ~ 1300 DEG C, sintering prepares target in sintering temperature, wherein, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one;
B the described target of preparation in step (a) and substrate are put into the vacuum cavity of pulsed laser deposition equipment by ();
C the distance of the described substrate in step (b) and described target is adjusted to 45mm ~ 95mm by (), the vacuum tightness of described vacuum cavity is adjusted to 1.0 × 10
-5pa ~ 1.0 × 10
-3pa, the flow of the working gas oxygen passed in described vacuum cavity is adjusted to 10sccm ~ 40sccm, the pressure of described oxygen is adjusted to 0.5Pa ~ 5Pa, described substrate temperature is adjusted to 250 DEG C ~ 750 DEG C, be 80mJ ~ 300mJ by the energy adjusting of the laser of described pulsed laser deposition equipment, then utilize described pulsed laser deposition equipment to be prepared into chemical formula for MeZr
2o
2n
2: xCe
3+described nitrogen zirconate light-emitting film, wherein, MeZr
2o
2n
2for matrix, Ce
3+for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one.
In one embodiment of this invention, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
A kind of electroluminescent device of the present invention, described electroluminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, and the material of described luminescent layer is chemical formula is MeZr
2o
2n
2: xCe
3+described nitrogen zirconate light-emitting film, wherein, MeZr
2o
2n
2for matrix, Ce
3+for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one.
In one embodiment of this invention, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
The preparation method of a kind of electroluminescent device of the present invention, comprises the following steps:
Substrate is clean, dry, for subsequent use;
Evaporation one deck anode layer on a surface of the described substrate of cleaning, and clean;
Be MeZr at deposited on silicon one deck chemical formula of described anode layer
2o
2n
2: xCe
3+described nitrogen zirconate light-emitting film, obtain luminescent layer; Wherein, MeZr
2o
2n
2for matrix, Ce
3+for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one;
Evaporation one deck cathode layer on the surface of described luminescent layer;
After above-mentioned steps completes, obtain described electroluminescent device.
In one embodiment of this invention, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
In one embodiment of this invention, the material of described substrate is glass, and the material of described anode layer is ITO conductive film, and the material of described cathode layer is Ag.
In sum, nitrogen zirconate light-emitting film of the present invention, electroluminescent device and the preparation method of the two, have the following advantages: nitrogen zirconate light-emitting film is with MeZr
2o
2n
2for matrix, to be entrained in the light emitting ionic Ce in matrix
3+as main luminescence center in light-emitting film, wherein, Me is any one in Mg, Ca, Sr, Ba and Zn, all has higher thermal stability and mechanical stability, and good optical transparence and lower phonon energy, can be light emitting ionic Ce
3+excellent crystal field is provided, thus produces less radiationless transition in the process of photovoltaic energy conversion; And light emitting ionic Ce
3+there is abundant energy level and the narrower spectral line of emission, and due to the shielding effect by 4f energy level out-shell electron, light emitting ionic Ce
3+the life time of the level longer, be more suitable for the launching centre as light-emitting film during photovoltaic energy conversion relative to other light emitting ionics.In addition, the preparation of this light-emitting film have employed pulsed laser deposition (PLD) method, and the sedimentation rate of the method is high, and the test period is short, is convenient to the clean of substrate; Processing parameter can regulate arbitrarily, the kind of target is not limited and can be higher the composition of maintenance target; Require low to substrate temperature, the light-emitting film of preparation is even and crystal property is good; The aftertreatment technologys such as annealing can also be saved.The present invention prepares nitrogen zirconate light-emitting film by adopting aforesaid method, not only increase luminous intensity and the luminous efficiency of light-emitting film, improve the structural stability of light-emitting film, and reduce preparation method's complexity, improve production efficiency, be more suitable for industrial applications.
Accompanying drawing explanation
The electroluminescence spectrum of the nitrogen zirconate light-emitting film of Fig. 1 embodiments of the invention 1.
The XRD curve of the nitrogen zirconate light-emitting film of Fig. 2 embodiments of the invention 1.
The structural representation of Fig. 3 electroluminescent device of the present invention.
The voltage of the electroluminescent device of the nitrogen zirconate light-emitting film of Fig. 4 use embodiment 1 of the present invention and electric current and brightness relationship figure.
Wherein, description of reference numerals is as follows:
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment mode described herein is only for explaining the present invention, is not intended to limit the present invention.
Embodiment 1
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 1 is MgZr
2o
2n
2: 0.03Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of MgO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.03mmol
2powder, after Homogeneous phase mixing, is the ceramic target of sintering preparation Φ 50 × 2mm under the condition of 1250 DEG C in sintering temperature;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 60mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 5.0 × 10
-4pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 20sccm, the pressure of oxygen is adjusted to 3Pa, substrate temperature is adjusted to 500 DEG C, be 150mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 200nm is nitrogen zirconate light-emitting film MgZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.03Ce
3+.
As shown in Figure 1, at the nitrogen magnesium zirconate MgZr of the doped with cerium adopting PLD method to prepare
2o
2n
2: 0.03Ce
3+in the electroluminescence spectrum (EL) of light-emitting film, this light-emitting film has very strong glow peak on 610nm position, and luminous intensity is very strong.
As shown in Figure 2, contrast X-ray diffraction (XRD) standard P DF card, in the XRD curve of above-mentioned cerium dopping nitrogen magnesium zirconate light-emitting film, is all peak crystallization of nitrogen magnesium zirconate, does not occur the light emitting ionic Ce of doping
3+and the diffraction peak of other impurity, namely show the nitrogen magnesium zirconate MgZr of doped with cerium prepared by this PLD method
2o
2n
2: 0.03Ce
3+light-emitting film has good crystalline quality, decreases mixing and interference of impurity, thus further increase the luminous intensity of this light-emitting film owing to improve purity.
Embodiment 2
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 2 is MgZr
2o
2n
2: 0.01Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of MgO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.01mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 900 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 45mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-3pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 10sccm, the pressure of oxygen is adjusted to 0.5Pa, substrate temperature is adjusted to 250 DEG C, be 80mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 80nm is nitrogen zirconate light-emitting film MgZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.01Ce
3+.
Embodiment 3
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 3 is MgZr
2o
2n
2: 0.05Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of MgO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.05mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 1300 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 95mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-5pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 40sccm, the pressure of oxygen is adjusted to 5Pa, substrate temperature is adjusted to 750 DEG C, be 300mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 400nm is nitrogen zirconate light-emitting film MgZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.05Ce
3+.
Embodiment 4
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 4 is CaZr
2o
2n
2: 0.03Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of CaO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.03mmol
2powder, after Homogeneous phase mixing, is the ceramic target of sintering preparation Φ 50 × 2mm under the condition of 1250 DEG C in sintering temperature;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 60mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 5.0 × 10
-4pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 20sccm, the pressure of oxygen is adjusted to 3Pa, substrate temperature is adjusted to 500 DEG C, be 150mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 200nm is nitrogen zirconate light-emitting film CaZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.03Ce
3+.
Embodiment 5
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 5 is CaZr
2o
2n
2: 0.01Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of CaO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.01mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 900 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 45mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-3pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 10sccm, the pressure of oxygen is adjusted to 0.5Pa, substrate temperature is adjusted to 250 DEG C, be 80mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 80nm is nitrogen zirconate light-emitting film CaZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.01Ce
3+.
Embodiment 6
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 6 is CaZr
2o
2n
2: 0.05Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of CaO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.05mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 1300 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 95mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-5pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 40sccm, the pressure of oxygen is adjusted to 5Pa, substrate temperature is adjusted to 750 DEG C, be 300mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 400nm is nitrogen zirconate light-emitting film CaZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.05Ce
3+.
Embodiment 7
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 7 is SrZr
2o
2n
2: 0.03Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of SrO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.03mmol
2powder, after Homogeneous phase mixing, is the ceramic target of sintering preparation Φ 50 × 2mm under the condition of 1250 DEG C in sintering temperature;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 60mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 5.0 × 10
-4pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 20sccm, the pressure of oxygen is adjusted to 3Pa, substrate temperature is adjusted to 500 DEG C, be 150mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 200nm is nitrogen zirconate light-emitting film SrZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.03Ce
3+.
Embodiment 8
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 8 is SrZr
2o
2n
2: 0.01Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of SrO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.01mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 900 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 45mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-3pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 10sccm, the pressure of oxygen is adjusted to 0.5Pa, substrate temperature is adjusted to 250 DEG C, be 80mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 80nm is nitrogen zirconate light-emitting film SrZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.01Ce
3+.
Embodiment 9
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 9 is SrZr
2o
2n
2: 0.05Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of SrO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.05mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 1300 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 95mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-5pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 40sccm, the pressure of oxygen is adjusted to 5Pa, substrate temperature is adjusted to 750 DEG C, be 300mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 400nm is nitrogen zirconate light-emitting film SrZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.05Ce
3+.
Embodiment 10
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 10 is BaZr
2o
2n
2: 0.03Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of BaO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.03mmol
2powder, after Homogeneous phase mixing, is the ceramic target of sintering preparation Φ 50 × 2mm under the condition of 1250 DEG C in sintering temperature;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 60mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 5.0 × 10
-4pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 20sccm, the pressure of oxygen is adjusted to 3Pa, substrate temperature is adjusted to 500 DEG C, be 150mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 200nm is nitrogen zirconate light-emitting film BaZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.03Ce
3+.
Embodiment 11
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 11 is BaZr
2o
2n
2: 0.01Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of BaO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.01mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 900 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 45mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-3pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 10sccm, the pressure of oxygen is adjusted to 0.5Pa, substrate temperature is adjusted to 250 DEG C, be 80mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 80nm is nitrogen zirconate light-emitting film BaZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.01Ce
3+.
Embodiment 12
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 12 is BaZr
2o
2n
2: 0.05Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of BaO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.05mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 1300 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 95mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-5pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 40sccm, the pressure of oxygen is adjusted to 5Pa, substrate temperature is adjusted to 750 DEG C, be 300mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 400nm is nitrogen zirconate light-emitting film BaZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.05Ce
3+.
Embodiment 13
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 13 is ZnZr
2o
2n
2: 0.03Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of ZnO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.03mmol
2powder, after Homogeneous phase mixing, is the ceramic target of sintering preparation Φ 50 × 2mm under the condition of 1250 DEG C in sintering temperature;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 60mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 5.0 × 10
-4pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 20sccm, the pressure of oxygen is adjusted to 3Pa, substrate temperature is adjusted to 500 DEG C, be 150mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 200nm is nitrogen zirconate light-emitting film ZnZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.03Ce
3+.
Embodiment 14
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 14 is ZnZr
2o
2n
2: 0.01Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of ZnO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.01mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 900 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 45mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-3pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 10sccm, the pressure of oxygen is adjusted to 0.5Pa, substrate temperature is adjusted to 250 DEG C, be 80mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 80nm is nitrogen zirconate light-emitting film ZnZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.01Ce
3+.
Embodiment 15
The chemical formula of the nitrogen zirconate light-emitting film of the present embodiment 15 is ZnZr
2o
2n
2: 0.05Ce
3+.
The preparation method of above-mentioned nitrogen zirconate light-emitting film, comprises the following steps:
The preparation of (a) target:
Take the ZrO of ZnO, 0.5mmol of 1mmol
2, 0.5mmol Zr
3n
4and the CeO of 0.05mmol
2powder, after Homogeneous phase mixing, the ceramic target of sintering preparation Φ 50 × 2mm under sintering temperature is 1300 DEG C of conditions;
The pre-treatment of (b) substrate:
The substrate of the glass material before pre-treatment is clean, dry, for subsequent use, on a surface of the substrate of this cleaning, evaporation one deck material is the anode layer of ITO conductive film, after being had by evaporation the substrate of this anode layer first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, carry out oxygen plasma treatment again, namely obtain pretreated substrate;
The preparation of (c) light-emitting film:
Above-mentioned ceramic target and substrate are put into the vacuum cavity of pulsed laser deposition equipment, the distance of this substrate and ceramic target is adjusted to 95mm, then with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is extracted into 1.0 × 10
-5pa, the flow of the working gas oxygen passed in vacuum cavity is adjusted to 40sccm, the pressure of oxygen is adjusted to 5Pa, substrate temperature is adjusted to 750 DEG C, be 300mJ by the energy adjusting of the laser of pulsed laser deposition equipment, sample that thickness is 400nm is nitrogen zirconate light-emitting film ZnZr then to utilize pulsed laser deposition equipment to be prepared into
2o
2n
2: 0.05Ce
3+.
Application Example
As shown in Figure 3, the electroluminescent device 1 in this application embodiment comprises: substrate 10, is located at the anode layer 20 on a surface of substrate 10, is located at the luminescent layer 30 on anode layer 20 surface, is located at the cathode layer 40 on luminescent layer 30 surface.
Wherein, the material of substrate 10 is glass, and the material of anode layer 20 is ITO conductive film, and the material of luminescent layer 30 is arbitrary nitrogen zirconate light-emitting film prepared by the preparation method in embodiment 1 ~ 15, and the material of cathode layer 40 is Ag.
The preparation method of above-mentioned electroluminescent device 1, comprises the following steps:
The substrate 10 of one glass material is provided, clean, dry, for subsequent use;
On a surface of the substrate 10 of cleaning, evaporation one deck ITO conductive film, obtains anode layer 20;
After being had by evaporation the substrate 10 of anode layer 20 first to carry out ultrasonic cleaning successively with acetone, dehydrated alcohol and deionized water, then carry out oxygen plasma treatment;
There is by evaporation after above-mentioned process the substrate 10 of anode layer 20 to put into vacuum cavity, at arbitrary nitrogen zirconate light-emitting film that anode layer 20 deposited on silicon one deck is prepared according to the preparation method in embodiment 1 ~ 15, obtain luminescent layer 30;
At luminescent layer 30 evaporation one deck Ag on the surface, obtain cathode layer 40.
After above-mentioned steps completes, obtain electroluminescent device 1.
As shown in Figure 4, adopting the nitrogen zirconate light-emitting film of embodiment 1 as in the voltage of the electroluminescent device 1 of the material of luminescent layer and electric current and brightness relationship figure, curve 1 is voltage and current density relation curve, device luminescence from 5.5V can be found out, curve 2 is voltage and brightness relationship curve, and high-high brightness is 110cd/m
2, show that this organic electroluminescence device just has larger luminosity when less drive current, there is the good characteristics of luminescence.
In sum, nitrogen zirconate light-emitting film of the present invention is with MeZr
2o
2n
2for matrix, to be entrained in the light emitting ionic Ce in matrix
3+as main luminescence center in light-emitting film, wherein, Me is any one in Mg, Ca, Sr, Ba and Zn, all has higher thermal stability and mechanical stability, and good optical transparence and lower phonon energy, can be light emitting ionic Ce
3+excellent crystal field is provided, thus produces less radiationless transition in the process of photovoltaic energy conversion; And light emitting ionic Ce
3+there is abundant energy level and the narrower spectral line of emission, and due to the shielding effect by 4f energy level out-shell electron, light emitting ionic Ce
3+the life time of the level longer, be more suitable for the launching centre as light-emitting film during photovoltaic energy conversion relative to other light emitting ionics.In addition, the preparation of this light-emitting film have employed pulsed laser deposition (PLD) method, and the sedimentation rate of the method is high, and the test period is short, is convenient to the clean of substrate; Processing parameter can regulate arbitrarily, the kind of target is not limited and can be higher the composition of maintenance target; Require low to substrate temperature, the light-emitting film of preparation is even and crystal property is good; The aftertreatment technologys such as annealing can also be saved.The present invention prepares nitrogen zirconate light-emitting film by adopting aforesaid method, not only increase luminous intensity and the luminous efficiency of light-emitting film, improve the structural stability of light-emitting film, and reduce preparation method's complexity, improve production efficiency, be more suitable for industrial applications.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.
Claims (10)
1. a nitrogen zirconate light-emitting film, is characterized in that, the chemical formula of described nitrogen zirconate light-emitting film is MeZr
2o
2n
2: xCe
3+; Wherein,
MeZr
2o
2n
2for matrix, Ce
3+for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one.
2. nitrogen zirconate light-emitting film according to claim 1, is characterized in that, x is 0.03.
3. nitrogen zirconate light-emitting film according to claim 1, is characterized in that, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
4. a preparation method for nitrogen zirconate light-emitting film, is characterized in that, comprises the following steps:
A () takes MeO, ZrO that mol ratio is 1:0.5:0.5:x
2, Zr
3n
4and CeO
2powder, after Homogeneous phase mixing, is that under the condition of 900 DEG C ~ 1300 DEG C, sintering prepares target in sintering temperature, wherein, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one;
B the described target of preparation in step (a) and substrate are put into the vacuum cavity of pulsed laser deposition equipment by ();
C the distance of the described substrate in step (b) and described target is adjusted to 45mm ~ 95mm by (), the vacuum tightness of described vacuum cavity is adjusted to 1.0 × 10
-5pa ~ 1.0 × 10
-3pa, the flow of the working gas oxygen passed in described vacuum cavity is adjusted to 10 sccm ~ 40sccm, the pressure of described oxygen is adjusted to 0.5Pa ~ 5Pa, described substrate temperature is adjusted to 250 DEG C ~ 750 DEG C, be 80mJ ~ 300mJ by the energy adjusting of the laser of described pulsed laser deposition equipment, then utilize described pulsed laser deposition equipment to be prepared into chemical formula for MeZr
2o
2n
2: xCe
3+described nitrogen zirconate light-emitting film, wherein, MeZr
2o
2n
2for matrix, Ce
3+for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one.
5. the preparation method of nitrogen zirconate light-emitting film according to claim 4, it is characterized in that, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
6. an electroluminescent device, described electroluminescent 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 chemical formula is MeZr
2o
2n
2: xCe
3+described nitrogen zirconate light-emitting film, wherein, MeZr
2o
2n
2for matrix, Ce
3+for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one.
7. electroluminescent device according to claim 6, is characterized in that, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
8. a preparation method for electroluminescent device, is characterized in that, comprises the following steps:
substrate is clean, dry, for subsequent use;
evaporation one deck anode layer on a surface of the described substrate of cleaning, and clean;
be MeZr at deposited on silicon one deck chemical formula of described anode layer
2
o
2
n
2
: xCe
3+
described nitrogen zirconate light-emitting film, obtain luminescent layer, wherein, MeZr
2
o
2
n
2
for matrix, Ce
3+
for light emitting ionic, the span of x to be 0.01 ~ 0.05, Me be in Mg, Ca, Sr, Ba or Zn any one;
evaporation one deck cathode layer on the surface of described luminescent layer;
After above-mentioned steps completes, obtain described electroluminescent device.
9. the preparation method of electroluminescent device according to claim 8, is characterized in that, the thickness of described nitrogen zirconate light-emitting film is 80nm ~ 400nm.
10. the preparation method of electroluminescent device according to claim 8, is characterized in that, the material of described substrate is glass, and the material of described anode layer is ITO conductive film, and the material of described cathode layer is Ag.
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|---|---|---|---|---|
| CN107287879A (en) * | 2016-03-31 | 2017-10-24 | 香港理工大学 | A kind of Luminous textile fabric preparation method based on laser annealing technique |
-
2013
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107287879A (en) * | 2016-03-31 | 2017-10-24 | 香港理工大学 | A kind of Luminous textile fabric preparation method based on laser annealing technique |
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