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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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000010409 thin film Substances 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 176
- 239000000758 substrate Substances 0.000 claims description 160
- 229910052757 nitrogen Inorganic materials 0.000 claims description 88
- 239000013077 target material Substances 0.000 claims description 66
- 238000000151 deposition Methods 0.000 claims description 53
- 230000008021 deposition Effects 0.000 claims description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 49
- 239000001301 oxygen Substances 0.000 claims description 49
- 229910052760 oxygen Inorganic materials 0.000 claims description 49
- 239000011521 glass Substances 0.000 claims description 34
- 238000004140 cleaning Methods 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000007747 plating Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 130
- 230000001105 regulatory effect Effects 0.000 description 51
- 239000000919 ceramic Substances 0.000 description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000009832 plasma treatment Methods 0.000 description 16
- 238000004506 ultrasonic cleaning Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005086 pumping Methods 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910017702 MgZr Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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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 invention relates to the technical field of semiconductor photoelectric materials, in particular to a nitrogen zirconate luminescent film, an electroluminescent device and preparation methods of the nitrogen zirconate luminescent film and the electroluminescent device.
Background
Thin film electroluminescent devices (TFELDs) have attracted much attention and developed rapidly due to their advantages of active luminescence, full-solid state, impact resistance, fast reaction, large viewing angle, wide application temperature, simple process, etc. Compared with the traditional electroluminescent device, the luminescent film has stronger superiority in the aspects of contrast, heat conduction, uniformity, adhesion with a substrate, outgassing rate and the like, so that the luminescent film with good performance has great significance in preparing the luminescent film.
The nitrogen zirconate luminescent film is a popular research material of an electroluminescent device, and is still continuously improved and researched at present, but the problems of complex process, expensive equipment, low luminescent intensity and the like of the prepared nitrogen zirconate luminescent film exist in the preparation of the luminescent film.
Disclosure of Invention
The invention aims to provide a nitrogen zirconate luminescent film, which is used for solving the problems of low luminescent intensity, complex preparation process and expensive preparation equipment of the nitrogen zirconate luminescent film in the prior art.
The invention also aims to provide a preparation method of the nitrogen zirconate luminescent film, which is used for preparing the nitrogen zirconate luminescent film.
The invention also aims to provide an electroluminescent device which comprises a substrate, an anode layer, a light-emitting layer and a cathode layer which are sequentially laminated, wherein the material of the light-emitting layer is the nitrogen zirconate light-emitting film.
The invention also aims to provide a preparation method of the electroluminescent device, which is used for preparing the electroluminescent device.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to a nitrogen zirconate luminescent film, which has a chemical formula of MeZr2O2N2：xCe3+(ii) a Wherein,
MeZr2O2N2as a base, Ce3+The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn.
In one embodiment of the present invention, x is 0.03.
In an embodiment of the invention, the thickness of the nitrogen zirconate light-emitting film is 80nm to 400 nm.
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) weighing a mixture with a molar ratio of 1: 0.5: 0.5: MeO, ZrO of x2、Zr3N4And CeO2Uniformly mixing powder, and sintering at the sintering temperature of 900-1300 ℃ to prepare a target material, wherein the value range of x is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn;
(b) placing the target material and the substrate prepared in the step (a) into a vacuum cavity of pulsed laser deposition equipment;
(c) adjusting the distance between the substrate and the target in the step (b) to 45-95 mm, and adjusting the vacuum degree of the vacuum cavity to 1.0 x 10-5Pa～1.0×10-3Pa, adjusting the flow of working gas oxygen introduced into the vacuum cavity to 10 sccm-40 sccm, adjusting the pressure of the oxygen to 0.5 Pa-5 Pa, adjusting the temperature of the substrate to 250 ℃ -750 ℃, adjusting the energy of laser of the pulse laser deposition equipment to 80 mJ-300 mJ, and then preparing the MeZr with the pulse laser deposition equipment2O2N2：xCe3+The nitrogen zirconate light-emitting film of (1), wherein MeZr2O2N2As a base, Ce3+The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn.
In an embodiment of the invention, the thickness of the nitrogen zirconate light-emitting film is 80nm to 400 nm.
The invention relates to an electroluminescent device, which comprises a substrate, an anode layer, a light-emitting layer and a cathode layer which are sequentially stacked, wherein the light-emitting layer is made of MeZr (MeZr) in a chemical formula2O2N2：xCe3+The nitrogen zirconate light-emitting film of (1), wherein MeZr2O2N2As a base, Ce3+The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn.
In an embodiment of the invention, the thickness of the nitrogen zirconate light-emitting film is 80nm to 400 nm.
The invention discloses a preparation method of an electroluminescent device, which comprises the following steps:
cleaning and drying the substrate for later use;
evaporating and plating an anode layer on one surface of the clean substrate, and cleaning;
depositing a layer of MeZr on the surface of the anode layer2O2N2：xCe3+The nitrogen zirconate luminescent film is obtained, and a luminescent layer is obtained; wherein, MeZr2O2N2As a base, Ce3+The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn;
evaporating a cathode layer on the surface of the luminous layer;
and obtaining the electroluminescent device after the steps are completed.
In an embodiment of the invention, the thickness of the nitrogen zirconate light-emitting film is 80nm to 400 nm.
In an embodiment of the invention, the substrate is made of glass, the anode layer is made of an ITO conductive film, and the cathode layer is made of Ag.
In summary, the nitrogen zirconate luminescent film, the electroluminescent device and the preparation methods thereof have the following advantages: the nitrogen zirconate luminescent film is made of MeZr2O2N2As a host, with a luminescent ion Ce doped in the host3+The luminescent film is used as a main luminescent center, wherein Me is any one of Mg, Ca, Sr, Ba and Zn, has high thermal stability and mechanical stability, good optical transparency and low phonon energy, and can be luminescent ion Ce3+Providing a good crystal field, thereby generating less radiationless transitions during the photoelectric energy conversion process; and the luminescent ion Ce3+Has rich energy level and narrow emission line, and the luminescent ion Ce is shielded by the electrons at the outer layer of the 4f energy level3+The energy level of (2) has longer service life, and is more suitable to be used as an emission center of a luminescent film in photoelectric energy conversion compared with other luminescent ions. In addition, the preparation of the luminescent film adopts a Pulse Laser Deposition (PLD) method, and the method has high deposition rate and short test period and is convenient for cleaning the substrate; process parametersCan be adjusted at will, has no limit on the types of the target materials and can keep the components of the target materials higher; the requirement on the temperature of the substrate is low, and the prepared luminescent film is uniform and has good crystallization property; and post-treatment processes such as annealing and the like can be saved. According to the invention, the nitrogen zirconate luminescent film is prepared by adopting the method, so that the luminous intensity and luminous efficiency of the luminescent film are improved, the structural stability of the luminescent film is improved, the complexity of the preparation method is reduced, the production efficiency is improved, and the method is more suitable for industrial application.
Drawings
FIG. 1 is an electroluminescence spectrum of a nitrogen zirconate light-emitting film of example 1 of the present invention.
FIG. 2 is an XRD plot of the nitrogen zirconate light-emitting film of example 1 of the present invention.
Fig. 3 is a schematic diagram of the structure of an electroluminescent device of the present invention.
FIG. 4 is a graph of voltage versus current and luminance for an electroluminescent device of the present invention using the nitrogen zirconate light-emitting film of example 1.
Wherein the reference numerals are as follows:
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are given by way of illustration only.
Example 1
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 1 is MgZr2O2N2：0.03Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of MgO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.03mmol of CeO2Uniformly mixing the powder, and sintering at 1250 ℃ to prepare a phi 50 multiplied by 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 60mm, and pumping the vacuum chamber to a vacuum degree of 5.0 × 10 by using a mechanical pump and a molecular pump-4Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 20sccm, regulating the pressure of the oxygen to 3Pa, regulating the temperature of the substrate to 500 ℃, regulating the energy of laser of the pulse laser deposition equipment to 150mJ, and preparing a sample with the thickness of 200nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film MgZr2O2N2：0.03Ce3+。
As shown in FIG. 1, magnesium zirconate nitride MgZr doped with cerium prepared by PLD method2O2N2：0.03Ce3+In an Electroluminescence (EL) spectrum of the light-emitting film, the light-emitting film has a strong light-emitting peak at a position of 610nm and has strong light-emitting intensity.
As shown in FIG. 2, in contrast to the standard PDF card of X-ray diffraction (XRD), the crystal peaks of magnesium zirconate nitride are observed in the XRD curve of the luminescent film of cerium-doped magnesium zirconate nitride, and doped luminescent ion Ce is not present3+And diffraction peaks of other impurities, namely indicating that the cerium-doped magnesium zirconate MgZr prepared by the PLD method2O2N2：0.03Ce3+The luminescent film has good crystallization quality, and the purity is improved, so that the doping and interference of impurities are reduced, and the luminescent intensity of the luminescent film is further improved.
Example 2
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 2 is MgZr2O2N2：0.01Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of MgO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.01mmol of CeO2Uniformly mixing the powder, and sintering at 900 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 45mm, and pumping the vacuum chamber to a vacuum degree of 1.0 × 10 by using a mechanical pump and a molecular pump-3Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 10sccm, regulating the pressure of the oxygen to 0.5Pa, regulating the temperature of the substrate to 250 ℃, regulating the energy of laser of the pulse laser deposition equipment to 80mJ, and preparing a sample with the thickness of 80nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film MgZr2O2N2：0.01Ce3+。
Example 3
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 3 is MgZr2O2N2：0.05Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of MgO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.05mmol of CeO2Uniformly mixing the powder, and sintering at 1300 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 95mm, and pumping the vacuum chamber to a vacuum degree of 1.0 × 10 by using a mechanical pump and a molecular pump-5Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 40sccm, regulating the pressure of the oxygen to 5Pa, regulating the temperature of the substrate to 750 ℃, regulating the energy of laser of the pulse laser deposition equipment to 300mJ, and preparing a sample with the thickness of 400nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film MgZr2O2N2：0.05Ce3+。
Example 4
The chemical formula of the nitrogen zirconate luminescent film of the embodiment 4 is CaZr2O2N2：0.03Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of CaO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.03mmol of CeO2Uniformly mixing the powder, and sintering at 1250 ℃ to prepare a phi 50 multiplied by 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 60mm, and pumping the vacuum chamber to a vacuum degree of 5.0 × 10 by using a mechanical pump and a molecular pump-4Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 20sccm, regulating the pressure of the oxygen to 3Pa, regulating the temperature of the substrate to 500 ℃, regulating the energy of laser of the pulse laser deposition equipment to 150mJ, and preparing a sample with the thickness of 200nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film CaZr2O2N2：0.03Ce3+。
Example 5
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 5 is CaZr2O2N2：0.01Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of CaO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.01mmol of CeO2Uniformly mixing the powder, and sintering at 900 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substratePutting into a vacuum chamber of a pulsed laser deposition device, adjusting the distance between the substrate and the ceramic target material to 45mm, and pumping the vacuum chamber to 1.0 × 10 with a mechanical pump and a molecular pump-3Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 10sccm, regulating the pressure of the oxygen to 0.5Pa, regulating the temperature of the substrate to 250 ℃, regulating the energy of laser of the pulse laser deposition equipment to 80mJ, and preparing a sample with the thickness of 80nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film CaZr2O2N2：0.01Ce3+。
Example 6
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 6 is CaZr2O2N2：0.05Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of CaO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.05mmol of CeO2Uniformly mixing the powder, and sintering at 1300 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum cavity of a pulse laser deposition deviceAdjusting the distance between the substrate and the ceramic target to 95mm, and pumping the vacuum degree of the vacuum chamber to 1.0 × 10 by using a mechanical pump and a molecular pump-5Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 40sccm, regulating the pressure of the oxygen to 5Pa, regulating the temperature of the substrate to 750 ℃, regulating the energy of laser of the pulse laser deposition equipment to 300mJ, and preparing a sample with the thickness of 400nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film CaZr2O2N2：0.05Ce3+。
Example 7
The formula of the nitrogen zirconate light-emitting film of the embodiment 7 is SrZr2O2N2：0.03Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of SrO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.03mmol of CeO2Uniformly mixing the powder, and sintering at 1250 ℃ to prepare a phi 50 multiplied by 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum cavity of a pulse laser deposition device, and adjusting the distance between the substrate and the ceramic target materialThe whole size is 60mm, and the vacuum degree of the vacuum cavity is pumped to 5.0 multiplied by 10 by a mechanical pump and a molecular pump-4Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 20sccm, regulating the pressure of the oxygen to 3Pa, regulating the temperature of the substrate to 500 ℃, regulating the energy of laser of the pulse laser deposition equipment to 150mJ, and preparing a sample with the thickness of 200nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film SrZr2O2N2：0.03Ce3+。
Example 8
The formula of the nitrogen zirconate light-emitting film of the embodiment 8 is SrZr2O2N2：0.01Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of SrO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.01mmol of CeO2Uniformly mixing the powder, and sintering at 900 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum cavity of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 45mm, and then using a mechanical pump and a molecular pump to control the vacuumThe vacuum degree of the cavity body is pumped to 1.0 multiplied by 10-3Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 10sccm, regulating the pressure of the oxygen to 0.5Pa, regulating the temperature of the substrate to 250 ℃, regulating the energy of laser of the pulse laser deposition equipment to 80mJ, and preparing a sample with the thickness of 80nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film SrZr2O2N2：0.01Ce3+。
Example 9
The formula of the nitrogen zirconate light-emitting film of the embodiment 9 is SrZr2O2N2：0.05Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of SrO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.05mmol of CeO2Uniformly mixing the powder, and sintering at 1300 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 95mm, and pumping the vacuum chamber to a vacuum degree of 1.0 × 10 by using a mechanical pump and a molecular pump-5Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 40sccm, regulating the pressure of the oxygen to 5Pa, regulating the temperature of the substrate to 750 ℃, regulating the energy of laser of the pulse laser deposition equipment to 300mJ, and preparing a sample with the thickness of 400nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film SrZr2O2N2：0.05Ce3+。
Example 10
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 10 is BaZr2O2N2：0.03Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of BaO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.03mmol of CeO2Uniformly mixing the powder, and sintering at 1250 ℃ to prepare a phi 50 multiplied by 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 60mm, and pumping the vacuum chamber to a vacuum degree of 5.0 × 10 by using a mechanical pump and a molecular pump-4Pa, working in a vacuum chamberAdjusting the flow of gas oxygen to 20sccm, adjusting the pressure of the oxygen to 3Pa, adjusting the temperature of the substrate to 500 ℃, adjusting the laser energy of the pulse laser deposition equipment to 150mJ, and preparing a sample with the thickness of 200nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film BaZr2O2N2：0.03Ce3+。
Example 11
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 11 is BaZr2O2N2：0.01Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of BaO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.01mmol of CeO2Uniformly mixing the powder, and sintering at 900 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 45mm, and pumping the vacuum chamber to a vacuum degree of 1.0 × 10 by using a mechanical pump and a molecular pump-3Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 10sccm, and introducing oxygenAdjusting the pressure of the gas to 0.5Pa, adjusting the temperature of the substrate to 250 ℃, adjusting the laser energy of the pulse laser deposition equipment to 80mJ, and preparing a sample with the thickness of 80nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film BaZr2O2N2：0.01Ce3+。
Example 12
The chemical formula of the nitrogen zirconate light-emitting film of the embodiment 12 is BaZr2O2N2：0.05Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of BaO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.05mmol of CeO2Uniformly mixing the powder, and sintering at 1300 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 95mm, and pumping the vacuum chamber to a vacuum degree of 1.0 × 10 by using a mechanical pump and a molecular pump-5Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 40sccm, regulating the pressure of the oxygen to 5Pa, and regulating the temperature of the substrateAdjusting the temperature to 750 ℃, adjusting the laser energy of the pulse laser deposition equipment to 300mJ, and preparing a sample with the thickness of 400nm by using the pulse laser deposition equipment, namely the nitrogen zirconate luminescent film BaZr2O2N2：0.05Ce3+。
Example 13
The chemical formula of the nitrogen zirconate luminescent film of the embodiment 13 is ZnZr2O2N2：0.03Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of ZnO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.03mmol of CeO2Uniformly mixing the powder, and sintering at 1250 ℃ to prepare a phi 50 multiplied by 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 60mm, and pumping the vacuum chamber to a vacuum degree of 5.0 × 10 by using a mechanical pump and a molecular pump-4Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 20sccm, regulating the pressure of the oxygen to 3Pa, regulating the temperature of the substrate to 500 ℃, and setting the pulse laser depositionThe energy of the prepared laser is adjusted to 150mJ, and then a sample with the thickness of 200nm, namely the nitrogen zirconate luminescent film ZnZr is prepared by utilizing pulse laser deposition equipment2O2N2：0.03Ce3+。
Example 14
The chemical formula of the nitrogen zirconate luminescent film of the embodiment 14 is ZnZr2O2N2：0.01Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of ZnO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.01mmol of CeO2Uniformly mixing the powder, and sintering at 900 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 45mm, and pumping the vacuum chamber to a vacuum degree of 1.0 × 10 by using a mechanical pump and a molecular pump-3Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 10sccm, regulating the pressure of the oxygen to 0.5Pa, regulating the temperature of the substrate to 250 ℃, regulating the energy of the laser of the pulsed laser deposition equipment to 80mJ, and thenPreparing a sample with the thickness of 80nm by using pulse laser deposition equipment, namely the nitrogen zirconate luminescent film ZnZr2O2N2：0.01Ce3+。
Example 15
The chemical formula of the nitrogen zirconate luminescent film of the embodiment 15 is ZnZr2O2N2：0.05Ce3+。
The preparation method of the nitrogen zirconate luminescent film comprises the following steps:
(a) preparing a target material:
1mmol of ZnO and 0.5mmol of ZrO were weighed20.5mmol of Zr3N4And 0.05mmol of CeO2Uniformly mixing the powder, and sintering at 1300 ℃ to prepare a phi 50X 2mm ceramic target material;
(b) pretreatment of the substrate:
cleaning a glass substrate before pretreatment, drying the glass substrate for later use, evaporating and plating an anode layer made of an ITO conductive film on one surface of the clean substrate, sequentially carrying out ultrasonic cleaning on the substrate evaporated with the anode layer by using acetone, absolute ethyl alcohol and deionized water, and then carrying out oxygen plasma treatment to obtain a pretreated substrate;
(c) preparing a luminescent film:
placing the ceramic target material and the substrate into a vacuum chamber of a pulse laser deposition device, adjusting the distance between the substrate and the ceramic target material to 95mm, and pumping the vacuum chamber to a vacuum degree of 1.0 × 10 by using a mechanical pump and a molecular pump-5Pa, regulating the flow of working gas oxygen introduced into the vacuum cavity to 40sccm, regulating the pressure of the oxygen to 5Pa, regulating the temperature of the substrate to 750 ℃, regulating the energy of laser of the pulse laser deposition equipment to 300mJ, and preparing the thickness by using the pulse laser deposition equipmentA sample with the thickness of 400nm is the nitrogen zirconate luminescent film ZnZr2O2N2：0.05Ce3+。
Application examples
As shown in fig. 3, the electroluminescent device 1 in the present application embodiment includes: the light-emitting device includes a substrate 10, an anode layer 20 provided on one surface of the substrate 10, a light-emitting layer 30 provided on a surface of the anode layer 20, and a cathode layer 40 provided on a surface of the light-emitting layer 30.
The substrate 10 is made of glass, the anode layer 20 is made of an ITO conductive film, the light-emitting layer 30 is made of any of the nitrogen zirconate light-emitting films prepared by the preparation methods in examples 1 to 15, and the cathode layer 40 is made of Ag.
The preparation method of the electroluminescent device 1 comprises the following steps:
providing a glass substrate 10, cleaning, drying and reserving;
evaporating an ITO conductive film on one surface of a clean substrate 10 to obtain an anode layer 20;
carrying out ultrasonic cleaning on the substrate 10 with the anode layer 20 by using acetone, absolute ethyl alcohol and deionized water in sequence, and then carrying out oxygen plasma treatment;
placing the treated substrate 10 with the anode layer 20 evaporated thereon into a vacuum chamber, and depositing a layer of any one of the nitrogen zirconate light-emitting films prepared by the preparation methods in the embodiments 1 to 15 on the surface of the anode layer 20 to obtain a light-emitting layer 30;
and evaporating a layer of Ag on the surface of the light-emitting layer 30 to obtain the cathode layer 40.
After the above steps are completed, the electroluminescent device 1 is obtained.
As shown in FIG. 4, in the voltage-current-luminance relationship chart of the electroluminescent device 1 using the nitrogen zirconate light-emitting film of example 1 as the material of the light-emitting layer, curve 1 is the voltage-current density relationshipCurve, it can be seen that the device starts emitting light from 5.5V, curve 2 is the voltage vs. luminance curve, and the maximum luminance is 110cd/m2The organic electroluminescent device has higher luminous brightness and good luminous characteristic when the driving current is smaller.
In summary, the nitrogen zirconate light-emitting film of the invention uses MeZr2O2N2As a host, with a luminescent ion Ce doped in the host3+The luminescent film is used as a main luminescent center, wherein Me is any one of Mg, Ca, Sr, Ba and Zn, has high thermal stability and mechanical stability, good optical transparency and low phonon energy, and can be luminescent ion Ce3+Providing a good crystal field, thereby generating less radiationless transitions during the photoelectric energy conversion process; and the luminescent ion Ce3+Has rich energy level and narrow emission line, and the luminescent ion Ce is shielded by the electrons at the outer layer of the 4f energy level3+The energy level of (2) has longer service life, and is more suitable to be used as an emission center of a luminescent film in photoelectric energy conversion compared with other luminescent ions. In addition, the preparation of the luminescent film adopts a Pulse Laser Deposition (PLD) method, and the method has high deposition rate and short test period and is convenient for cleaning the substrate; the technological parameters can be adjusted at will, the types of the target materials are not limited, and the components of the target materials can be kept high; the requirement on the temperature of the substrate is low, and the prepared luminescent film is uniform and has good crystallization property; and post-treatment processes such as annealing and the like can be saved. According to the invention, the nitrogen zirconate luminescent film is prepared by adopting the method, so that the luminous intensity and luminous efficiency of the luminescent film are improved, the structural stability of the luminescent film is improved, the complexity of the preparation method is reduced, the production efficiency is improved, and the method is more suitable for industrial application.
The above-mentioned embodiments are merely preferred examples of the present invention, and not intended to limit the present invention, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, so that the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The nitrogen zirconate luminescent film is characterized by having a chemical formula of MeZr2O2N2：xCe3+(ii) a Wherein,
MeZr2O2N2as a base, Ce3+The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn.
2. The nitrogen zirconate light-emitting film according to claim 1, wherein x is 0.03.
3. The nitrogen zirconate light-emitting film according to claim 1, wherein the thickness of the nitrogen zirconate light-emitting film is from 80nm to 400 nm.
4. The preparation method of the nitrogen zirconate luminescent film is characterized by comprising the following steps of:
(a) weighing a mixture with a molar ratio of 1: 0.5: 0.5: MeO, ZrO of x2、Zr3N4And CeO2Uniformly mixing powder, and sintering at the sintering temperature of 900-1300 ℃ to prepare a target material, wherein the value range of x is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn;
(b) placing the target material and the substrate prepared in the step (a) into a vacuum cavity of pulsed laser deposition equipment;
(c) adjusting the distance between the substrate and the target in the step (b) to be 45-95 mm, and adjusting the vacuum degree of the vacuum cavity to be 1.0 multiplied by 10-5Pa~1.0×10-3Pa, adjusting the flow of working gas oxygen introduced into the vacuum cavity to 10 sccm-40 sccm, adjusting the pressure of the oxygen to 0.5 Pa-5 Pa, adjusting the temperature of the substrate to 250 ℃ to 750 ℃, adjusting the energy of laser of the pulse laser deposition equipment to 80 mJ-300 mJ, and then preparing the MeZr with the pulse laser deposition equipment2O2N2：xCe3+The nitrogen zirconate light-emitting film of (1), wherein MeZr2O2N2As a base, Ce3+The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn.
5. The method for preparing the nitrogen zirconate light-emitting film according to claim 4, wherein the thickness of the nitrogen zirconate light-emitting film is 80nm to 400 nm.
6. An electroluminescent device comprises a substrate, an anode layer, a light-emitting layer and a cathode layer which are sequentially stacked, and is characterized in that the light-emitting layer is made of MeZr2O2N2：xCe3+The nitrogen zirconate light-emitting film of (1), wherein MeZr2O2N2As a base, Ce3+The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn.
7. The electroluminescent device according to claim 6, wherein the thickness of the nitrogen zirconate luminescent film is 80nm to 400 nm.
8. A method for preparing an electroluminescent device is characterized by comprising the following steps:
cleaning and drying the substrate for later use;
evaporating and plating an anode layer on one surface of the clean substrate, and cleaning;
depositing a layer of MeZr on the surface of the anode layer
2
O
2
N
2
：xCe
3+
The nitrogen zirconate luminescent film is obtained, namely a luminescent layer, wherein, MeZr
2
O
2
N
2
As a base, Ce
3+
The luminescent ion is X, the value range of X is 0.01-0.05, and Me is any one of Mg, Ca, Sr, Ba or Zn;
evaporating a cathode layer on the surface of the luminous layer;
and obtaining the electroluminescent device after the steps are completed.
9. The method for preparing an electroluminescent device according to claim 8, wherein the thickness of the nitrogen zirconate luminescent film is 80nm to 400 nm.
10. The method of claim 8, wherein the substrate is made of glass, the anode layer is made of an ITO conductive film, and the cathode layer is made of Ag.
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