Material design method for ferroelectric non-volatile dynamic regulation and control of metal ion luminescence
By performing transition metal ion doping and multiple growth on ε-Ga2O3 material, using ferroelectrodepolation flip and ion coordination changes, the production of nonvolatile regulated metal ion luminescent materials is achieved, and the external field of existing luminescent materials is solved. The issue of regulation that can only be instantaneously regulated has expanded the application of semiconductor dynamic luminescence display field.
Patent Information
- Application Number
- CN202411282847.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-13
- Publication Date
- 2024-12-17
AI Technical Summary
The external field regulation of luminescent properties of existing luminescent materials can only achieve instantaneous regulation, but cannot achieve nonvolatile regulation.
By growing ε-Ga2O3 material on the substrate, doping transition metal ion, and performing the second ε-Ga2O3 material growth, forming a nonvolatile regulated metal ion luminescent material, which is achieved by using ferroelectrode polarization flip and ion coordination changes Nonvolatile regulation.
The nonvolatile luminescence characteristics of doped metal ions are realized, avoiding the problem of returning to the initial state after the field is removed, and expanding the application prospects in the field of semiconductor dynamic luminescence display.
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Figure CN119144322A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of non-volatile regulated metal ion luminescent materials, and in particular to a non-volatile regulated metal ion luminescent material and a preparation method thereof. Background Art
[0002] Since the successful preparation of light-emitting diode devices in 1962, the application scenarios of semiconductor materials in the field of light-emitting display have been increasing. However, with the continuous improvement of the requirements for device integration and multifunctionality, traditional light-emitting devices based on semiconductor materials lack the freedom of external field adjustment, which limits the application of light-emitting diodes.
[0003] It is difficult to dynamically control the emission wavelength of light-emitting devices based on traditional semiconductor materials. In recent years, a large number of studies have been conducted on using the different responses of semiconductor materials to external fields to adjust their emission characteristics. For example, it has been found that "mechanically controlled luminescence" can be achieved by applying stress to the host material, and "piezoelectrically controlled luminescence" can be achieved by applying an external electric field to a host material with piezoelectric properties. However, these external field-controlled luminescence properties are usually transient, and when the external field is removed, the luminescence properties of the material will return to their initial state. Summary of the invention
[0004] In view of the above problems, an embodiment of the present invention provides a method for preparing a non-volatile controllable metal ion luminescent material, which is used to solve the technical problem that the external field control of the luminescent properties of existing luminescent materials can only achieve instantaneous control.
[0005] According to one aspect of an embodiment of the present invention, a method for manufacturing a non-volatile controllable metal ion luminescent material is provided, comprising:
[0006] Performing a first ε-Ga2O3 material growth on the substrate to obtain a first semi-finished product having a first target thickness;
[0007] Doping the material growth surface of the first semi-finished product with transition metal ions to obtain a second semi-finished product having a metal ion doped layer;
[0008] A second ε-Ga2O3 material growth is performed on the doped surface of the second semi-finished product to obtain a non-volatile controllable metal ion light-emitting material with a second target thickness.
[0009] In an optional manner, the step of performing a first growth of ε-Ga2O3 material on a substrate to obtain a first semi-finished product having a first target thickness includes:
[0010] placing the sapphire substrate into a reaction chamber;
[0011] Placing a gas source bottle filled with a first target gas source in a temperature-adjustable device so that the gas outputted from the gas source bottle meets a first target vapor pressure; the first target gas source is hydrogen;
[0012] Heating the internal temperature of the reaction chamber to a first target temperature; the first target temperature ranges from 600° C. to 700° C.;
[0013] Trimethylgallium, high-purity oxygen, and high-purity water are introduced into the reaction chamber to perform initial material growth on the sapphire substrate to obtain the first semi-finished product with a first target thickness.
[0014] In an optional manner, the step of doping the material growth surface of the first semi-finished product with transition metal ions to obtain a second semi-finished product having a metal ion doped layer includes:
[0015] Filling a first target amount of argon gas into the vacuum reaction chamber;
[0016] placing a transition metal into the reaction chamber;
[0017] Applying a direct current voltage between the transition metal and the inner wall of the reaction chamber to generate a magnetron type abnormal glow discharge to ionize the argon gas;
[0018] The ionized argon gas is accelerated and bombards the transition metal surface of the cathode, thereby sputtering atoms on the transition metal surface and depositing them on the first semi-finished product to form the second semi-finished product having the metal ion doping layer.
[0019] In an optional manner, the step of performing a second ε-Ga2O3 material growth on the doped surface of the second semi-finished product to obtain a non-volatile controllable metal ion light-emitting material having a second target thickness includes:
[0020] placing the second semi-finished product into the reaction chamber;
[0021] Placing a gas source bottle filled with a second target gas source in the temperature-adjustable device so that the gas output by the gas source bottle meets a second target vapor pressure; the second target gas source is hydrogen;
[0022] Heating the internal temperature of the reaction chamber to a second target temperature; the second target temperature ranges from 600° C. to 700° C.;
[0023] Trimethylgallium, high-purity oxygen and high-purity water are introduced into the reaction chamber to perform material growth again on the second semi-finished product to obtain a non-volatile controllable metal ion luminescent material with a second target thickness.
[0024] In an optional manner, the atomic structure crystal space group of the ε-Ga2O3 is Pna21, which has the characteristic of ferroelectric polarization reversal.
[0025] In an optional manner, when transition metal ion doping is performed, the ε-Ga2O3 undergoes ferroelectric polarization reversal, and the coordination of some Ga atoms in the trimethylgallium changes from tetracoordinate to hexacoordinate or from hexacoordinate to tetracoordinate.
[0026] In an optional manner, when transition metal ion doping is performed, a metal ion doping layer is formed, wherein the metal ion doping layer has a plurality of electron orbital atomic configurations, and the orbits are respectively denoted as t2, e, e g and t 2g , where t2 and e represent the energy level splitting of the d electrons of the transition metal ion under tetrahedral (abbreviated as tet) coordination; e g ,t 2g Representing the energy level splitting of the d electrons of the metal ion under the octahedral (oct) coordination, the atomic configuration of the electronic orbital of the transition metal under different coordination conditions is recorded as:
[0027] When the orbital is t2, the corresponding atomic configuration is (d xy , d xz , d yz );
[0028] When the orbital is e, the corresponding atomic configuration is (d x2-y2 , d z2 );
[0029] When the orbital is e g When the corresponding atomic configuration is (d x2-y2 , d z2 );
[0030] When the orbit is t 2g When the corresponding atomic configuration is (d xy , d xz , d yz ).
[0031] The present application also proposes a non-volatile regulated metal ion luminescent material, which is manufactured according to the manufacturing method of the non-volatile regulated metal ion luminescent material as described above, and the non-volatile regulated metal ion luminescent material includes a substrate, a first ε-Ga2O3 layer, a metal ion doping layer and a second ε-Ga2O3 layer stacked in sequence.
[0032] The present invention proposes a method for making a new non-volatile regulated metal ion luminescent material based on ε-Ga2O3 ferroelectric material. Through the design and production of ε-Ga2O3, the finished non-volatile regulated metal ion luminescent material not only changes in polarization direction before and after the ferroelectric polarization is flipped, but also changes in ion coordination. Utilizing this unique characteristic, the "non-volatile regulated luminescence" property of doped metal ions is realized, and the initial state will not be restored due to the removal of the external field, thus having new application prospects in the field of semiconductor dynamic luminescent display. The technical solution of the present invention solves the technical problem that the luminescence properties of existing luminescent materials can only be regulated instantaneously by external field regulation.
[0033] The above description is only an overview of the technical solution of the embodiment of the present invention. In order to more clearly understand the technical means of the embodiment of the present invention, it can be implemented according to the contents of the specification. In addition, in order to make the above and other purposes, features and advantages of the embodiment of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are specifically illustrated below. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] The accompanying drawings are only used to illustrate the embodiments of the present invention and should not be considered as limiting the present invention. In the entire drawings, the same reference symbols represent the same components.
[0035] Figure 1 : A schematic flow chart of the method for preparing the non-volatile regulated metal ion luminescent material provided by the present invention is shown.
[0036] Figure 2 : A schematic diagram of the atomic structure of the non-volatile regulated metal ion luminescent material provided by the present invention is shown.
[0037] Figure 3 : A schematic diagram showing the atomic migration path and potential barrier for polarization reversal of non-volatile regulation of metal ion luminescent materials provided by the present invention.
[0038] Figure 4 : A schematic diagram of the electronic orbital atomic configuration of the transition metal in the non-volatile regulated metal ion luminescent material provided by the present invention under different coordination conditions is shown. DETAILED DESCRIPTION
[0039] Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein.
[0040] The present application provides a method for preparing a non-volatile controllable metal ion luminescent material, which is used to solve the technical problem that the luminescent properties of existing luminescent materials can only be controlled instantaneously by external field control.
[0041] In an alternative embodiment, Figure 1 A flow chart of a method for preparing a non-volatile metal ion luminescent material is shown. A method for preparing a non-volatile metal ion luminescent material comprises:
[0042] Step S1, performing a first growth of ε-Ga2O3 material on a substrate to obtain a first semi-finished product having a first target thickness.
[0043] Optionally, the substrate is a sapphire substrate, and the step of performing a first growth of ε-Ga2O3 material on the substrate to obtain a first semi-finished product having a first target thickness comprises:
[0044] Step S11, placing the sapphire substrate into a reaction chamber.
[0045] The size of the sapphire substrate is determined according to the size of the finished product of the non-volatile metal ion luminescent material actually required, and the reaction chamber needs to be sealed, ventilated and capable of high-temperature heating.
[0046] Step S12, placing a gas source bottle filled with a first target gas source in a temperature-adjustable device so that the gas output from the gas source bottle meets a first target vapor pressure; the first target gas source is hydrogen.
[0047] At this time, hydrogen acts as a carrier to carry the reactants, which can avoid situations such as insufficient fluidity of the reactants that affect the reaction rate.
[0048] Step S13, heating the internal temperature of the reaction chamber to a first target temperature; the first target temperature ranges from 600°C to 700°C.
[0049] Further, the first target temperature may preferably be 650°C.
[0050] Step S14, introducing trimethylgallium, high-purity oxygen, and high-purity water into the reaction chamber to perform initial material growth on the sapphire substrate to obtain the first semi-finished product with a first target thickness.
[0051] Among them, trimethylgallium is ε-Ga2O3, and the first material grown at this time is the first ε-Ga2O3 layer, which constitutes the first semi-finished product with the sapphire substrate. The first target thickness at this time includes the thickness of the first ε-Ga2O3 layer and the thickness of the sapphire substrate. Since the thickness of the sapphire substrate can be determined when the sapphire substrate is placed, when the first target thickness is confirmed, the thickness of the first ε-Ga2O3 layer grown by the first material is determined. At this time, the thickness can be pre-established in the laboratory with a time-growth thickness curve related to the growth thickness, carrier gas concentration, internal temperature and other changing parameters, that is, under certain carrier gas concentration and internal temperature conditions, the internal growth thickness can be determined by timing without additional measurement.
[0052] Step S2, doping the material growth surface of the first semi-finished product with transition metal ions to obtain a second semi-finished product having a metal ion doping layer;
[0053] Optionally, in an optional embodiment, the step of doping the material growth surface of the first semi-finished product with transition metal ions to obtain a second semi-finished product having a metal ion doped layer includes:
[0054] Step S21, filling the vacuum reaction chamber with a first target amount of argon gas.
[0055] At this time, argon gas is present as a reactant.
[0056] Step S22: placing a transition metal into the reaction chamber.
[0057] Among them, the transition metal can be Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and other metals.
[0058] Step S23, applying a DC voltage between the transition metal and the inner wall of the reaction chamber to generate a magnetron type abnormal glow discharge to ionize the argon gas.
[0059] The specific value of the DC voltage is selected according to the conditions of the reaction chamber and the type of transition metal. The voltage can be set based on actual measurement data or experience so that the argon gas is ionized under the action of the magnetic field generated by the DC voltage.
[0060] Step S24: The ionized argon gas is accelerated and bombards the transition metal surface of the cathode, thereby sputtering atoms on the transition metal surface and depositing them on the first semi-finished product to form the second semi-finished product having the metal ion doping layer.
[0061] When the first ε-Ga2O3 layer of the first semi-finished product is sputtered to atoms, the ferroelectric polarization reversal occurs, accompanied by changes in the cation coordination, thereby achieving dynamic adjustment of the luminescence properties of metal ions. At this time, the structure of the doped layer obtained by the ferroelectric polarization reversal can be referred to Figure 2 As shown, atoms with different coordination are distinguished by colors to illustrate the polarization reversal process.
[0062] Step S3: performing a second ε-Ga2O3 material growth on the doped surface of the second semi-finished product to obtain a non-volatile controllable metal ion light-emitting material with a second target thickness.
[0063] Optionally, the step of performing a second ε-Ga2O3 material growth on the doped surface of the second semi-finished product to obtain a non-volatile regulated metal ion luminescent material having a second target thickness includes:
[0064] Step S31, placing the second semi-finished product into the reaction chamber.
[0065] Step S32, placing a gas source bottle filled with a second target gas source in the temperature-adjustable device, so that the gas output by the gas source bottle meets a second target vapor pressure; the second target gas source is hydrogen.
[0066] At this time, hydrogen is used as a carrier, and the second target vapor pressure can be flexibly set according to experimental conditions to achieve the purpose of effectively transporting the reactants.
[0067] Step S33, heating the internal temperature of the reaction chamber to a second target temperature; the second target temperature ranges from 600°C to 700°C.
[0068] Furthermore, the second target temperature is 650°C.
[0069] Step S34, introducing trimethylgallium, high-purity oxygen and high-purity water into the reaction chamber to perform material growth again on the second semi-finished product to obtain a non-volatile controllable metal ion luminescent material with a second target thickness.
[0070] At this time, the material is grown again to obtain the second ε-Ga2O3 layer, and the final non-volatile regulated metal ion luminescent material includes a substrate, a first ε-Ga2O3 layer, a metal ion doping layer and a second ε-Ga2O3 layer stacked in sequence.
[0071] The present invention introduces ε-Ga2O3 ferroelectric material by designing a new non-volatile adjustable metal ion luminescent material. Through careful design and preparation of ε-Ga2O3, the final non-volatile adjustable metal ion luminescent material not only changes the polarization direction but also changes the ion coordination before and after the ferroelectric polarization is flipped. Utilizing this unique characteristic, the "non-volatile adjustable luminescence" characteristic of doped metal ions is successfully realized, avoiding the problem of returning to the initial state after the external field is removed. This innovation is expected to open up new application prospects in the field of semiconductor dynamic luminescent display, and effectively solve the technical limitation that existing luminescent materials can only achieve instantaneous regulation.
[0072] Optionally, the atomic structure crystal space group of the ε-Ga2O3 is Pna21, which has the characteristic of ferroelectric polarization reversal.
[0073] Optionally, refer to Figure 3 As shown, when transition metal ion doping is performed, the trimethylgallium undergoes ferroelectric polarization reversal, and the coordination of some Ga atoms in the ε-Ga2O3 changes from four-coordinate to six-coordinate or from six-coordinate to four-coordinate.
[0074] It should be noted that the above Figure 3 The direction of the polarization reversal path can be bidirectional. As long as the external electric field provided is higher than the coercive field, the switching of different polarization states of the ferroelectric material ε-Ga2O3 can be achieved. In different polarization states, the coordination number of metal ions is different and the emission band is different.
[0075] Optionally, when the transition metal ion doping is performed, a metal ion doping layer is formed, wherein the metal ion doping layer has a plurality of electron orbital atomic configurations, and the orbits are respectively denoted as t2, e, e g and t 2g , where t2 and e represent the energy level splitting of the d electrons of the transition metal ion under tetrahedral (abbreviated as tet) coordination; e g ,t 2g Representing the energy level splitting of the d electrons of the metal ion under the octahedral (oct) coordination, the atomic configuration of the electronic orbital of the transition metal under different coordination conditions is recorded as:
[0076] When the orbital is t2, the corresponding atomic configuration is (d xy , d xz , d yz );
[0077] When the orbital is e, the corresponding atomic configuration is (d x2-y2 , d z2 );
[0078] When the orbital is eg When the corresponding atomic configuration is (d x2-y2 , d z2 );
[0079] When the orbit is t 2g When the corresponding atomic configuration is (d xy , d xz , d yz ).
[0080] The present application also proposes a non-volatile metal ion luminescent material, which is manufactured according to the manufacturing method of the non-volatile metal ion luminescent material as described above:
[0081] The non-volatile metal ion light-emitting material comprises a substrate, a first ε-Ga2O3 layer, a metal ion doping layer and a second ε-Ga2O3 layer which are stacked in sequence.
[0082] Since the above-mentioned non-volatile metal ion luminescent material is manufactured by adopting the manufacturing method of non-volatile metal ion luminescent material, all the schemes and beneficial effects of the manufacturing method of non-volatile metal ion luminescent material are included and will not be repeated here.
[0083] Optionally, the material of the metal ion doping layer is a doping layer formed by doping the third period transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn on ε-Ga2O3. The luminescence process of the non-volatile regulated metal ion luminescent material produced therefrom comes from the d electrons of the transition metal and is regulated by the coordination field.
[0084] The algorithms or displays provided herein are not inherently related to any particular computer, virtual system or other device. In addition, the embodiments of the present invention are not directed to any particular programming language.
[0085] In the description provided herein, a large number of specific details are described. However, it is understood that embodiments of the present invention can be practiced without these specific details. Similarly, in order to simplify the present invention and help understand one or more of the various inventive aspects, in the above description of exemplary embodiments of the present invention, the various features of the embodiments of the present invention are sometimes grouped together into a single embodiment, figure, or description thereof. Wherein, the claims that follow the specific embodiment are hereby expressly incorporated into the specific embodiment, wherein each claim itself is a separate embodiment of the present invention.
[0086] Those skilled in the art will appreciate that the modules in the devices in the embodiments may be adaptively changed and arranged in one or more devices different from the embodiments. The modules or units or components in the embodiments may be combined into one module or unit or component, and further may be divided into a plurality of submodules or subunits or subcomponents. Except that at least some of such features and / or processes or units are mutually exclusive.
[0087] It should be noted that the above embodiments illustrate the present invention rather than limit it, and that those skilled in the art may devise alternative embodiments without departing from the scope of the appended claims. In the claims, any reference symbol between brackets shall not be construed as a limitation on the claims. The word "comprising" does not exclude the presence of elements or steps not listed in the claims. The word "one" or "an" preceding an element does not exclude the presence of a plurality of such elements. The present invention may be implemented by means of hardware comprising a number of different elements and by means of a suitably programmed computer. In a unit claim enumerating a number of devices, several of these devices may be embodied by the same hardware item. The use of the words first, second, and third, etc. does not indicate any order. These words may be interpreted as names. The steps in the above embodiments, unless otherwise specified, should not be understood as limitations on the order of execution.
Claims
1. A method for preparing a non-volatile controllable metal ion luminescent material, characterized in that: include: Performing a first ε-Ga2O3 material growth on the substrate to obtain a first semi-finished product having a first target thickness; Doping the material growth surface of the first semi-finished product with transition metal ions to obtain a second semi-finished product having a metal ion doped layer; A second ε-Ga2O3 material growth is performed on the doped surface of the second semi-finished product to obtain a non-volatile controllable metal ion light-emitting material with a second target thickness.
2. The method for preparing the nonvolatile controllable metal ion luminescent material according to claim 1, characterized in that: The substrate is a sapphire substrate, and the step of performing a first growth of ε-Ga2O3 material on the substrate to obtain a first semi-finished product having a first target thickness comprises: placing the sapphire substrate into a reaction chamber; Placing a gas source bottle filled with a first target gas source in a temperature-adjustable device so that the gas outputted from the gas source bottle meets a first target vapor pressure; the first target gas source is hydrogen; Heating the internal temperature of the reaction chamber to a first target temperature; the first target temperature ranges from 600° C. to 700° C.; Trimethylgallium, high-purity oxygen, and high-purity water are introduced into the reaction chamber to perform initial material growth on the sapphire substrate to obtain the first semi-finished product with a first target thickness.
3. The method for preparing the nonvolatile controllable metal ion luminescent material according to claim 1, characterized in that: The step of doping the material growth surface of the first semi-finished product with transition metal ions to obtain a second semi-finished product having a metal ion doped layer comprises: Filling a first target amount of argon gas into the vacuum reaction chamber; placing a transition metal into the reaction chamber; Applying a direct current voltage between the transition metal and the inner wall of the reaction chamber to generate a magnetron type abnormal glow discharge to ionize the argon gas; The ionized argon gas is accelerated and bombards the transition metal surface of the cathode, thereby sputtering atoms on the transition metal surface and depositing them on the first semi-finished product to form the second semi-finished product having the metal ion doping layer.
4. The method for preparing the nonvolatile controllable metal ion luminescent material according to claim 1, characterized in that: The step of performing a second ε-Ga2O3 material growth on the doped surface of the second semi-finished product to obtain a non-volatile controllable metal ion light-emitting material having a second target thickness comprises: placing the second semi-finished product into the reaction chamber; Placing a gas source bottle filled with a second target gas source in the temperature-adjustable device so that the gas output by the gas source bottle meets a second target vapor pressure; the second target gas source is hydrogen; Heating the internal temperature of the reaction chamber to a second target temperature; the second target temperature ranges from 600° C. to 700° C.; Trimethylgallium, high-purity oxygen and high-purity water are introduced into the reaction chamber to perform material growth again on the second semi-finished product to obtain a non-volatile controllable metal ion luminescent material with a second target thickness.
5. The method for preparing the nonvolatile controllable metal ion luminescent material according to claim 1, characterized in that: The atomic structure crystal space group of the ε-Ga2O3 is Pna21, and has the characteristic of ferroelectric polarization reversal.
6. The method for preparing the nonvolatile controllable metal ion luminescent material according to claim 5, characterized in that: When doping with transition metal ions is performed, the ε-Ga2O3 undergoes ferroelectric polarization reversal, and the coordination of some Ga atoms in the ε-Ga2O3 changes from four-coordinate to six-coordinate or from six-coordinate to four-coordinate.
7. The method for preparing the nonvolatile controllable metal ion luminescent material according to claim 5, characterized in that: When transition metal ion doping is performed, a metal ion doping layer is formed. The metal ion doping layer has multiple electron orbital atomic configurations, and the orbits are respectively denoted as t2, e, e g and t 2g , where t2 and e represent the energy level splitting of the d electrons of the transition metal ion under tetrahedral (abbreviated as tet) coordination; e g ,t 2g Representing the energy level splitting of the d electrons of the metal ion under the octahedral (oct) coordination, the atomic configuration of the electronic orbital of the transition metal under different coordination conditions is recorded as: When the orbital is t2, the corresponding atomic configuration is (d xy , d xz , d yz ); When the orbital is e, the corresponding atomic configuration is (d x2-y2 , d z2 ); When the orbital is e g When the corresponding atomic configuration is (d x2-y2 , d z2 ); When the orbit is t 2g When the corresponding atomic configuration is (d xy , d xz , d yz ).
8. A non-volatile regulated metal ion luminescent material, characterized in that: The non-volatile regulated metal ion luminescent material is manufactured according to the manufacturing method of any one of claims 1-7, wherein the non-volatile regulated metal ion luminescent material comprises a substrate, a first ε-Ga2O3 layer, a metal ion doping layer and a second ε-Ga2O3 layer which are stacked in sequence.