CN114530540A - Color conversion layer and preparation method thereof - Google Patents

Color conversion layer and preparation method thereof Download PDF

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Publication number
CN114530540A
CN114530540A CN202210154312.2A CN202210154312A CN114530540A CN 114530540 A CN114530540 A CN 114530540A CN 202210154312 A CN202210154312 A CN 202210154312A CN 114530540 A CN114530540 A CN 114530540A
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quantum dots
phase
phase structure
color conversion
conversion layer
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CN114530540B (en
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庄文荣
孙明
卢敬权
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Dongguan HCP Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/505Wavelength conversion elements characterised by the shape, e.g. plate or foil
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008Processes
    • H01L2933/0033Processes relating to semiconductor body packages
    • H01L2933/0041Processes relating to semiconductor body packages relating to wavelength conversion elements
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

The invention discloses a color conversion layer and a preparation method thereof, wherein the preparation method comprises the following steps: (1) providing a phase separation structure; (2) corroding the phase separation structure to enable the phase separation structure to have a porous structure; (3) and filling the porous structure with first quantum dots. The preparation method of the color conversion layer provided by the invention provides a phase separation structure and corrodes the phase separation structure to form a porous structure, and then the porous structure is filled with the first quantum dots, if the first quantum dots with the same size are filled, the light with the same color is enhanced, and if two or more than two first quantum dots are filled, the light with different colors can be matched.

Description

Color conversion layer and preparation method thereof
Technical Field
The invention relates to the technical field of LED chips, in particular to a color conversion layer and a preparation method thereof.
Background
The LED chip has better energy-saving effect and higher brightness, and is used in various industries of production and life. In the prior art, LED chips are usually made of gallium nitride, and chips using gallium nitride can only emit blue light and green light, but cannot emit light of other colors, such as red light, and cannot meet application requirements. Therefore, when the LED is applied to the display field, the full-color picture can be displayed only by matching the red light chip of the AlInGaP quaternary system. However, in small-pitch or micro-pitch LED displays, the cost of producing flip red chips with low yield accounts for a large proportion, and the chips are difficult to further shrink, so an alternative to color conversion is proposed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a color conversion layer, which comprises the following steps:
(1) providing a phase separation structure;
(2) corroding the phase separation structure to make the phase separation structure have a porous structure;
(3) and filling the porous structure with first quantum dots.
Preferably, in step (1), the phase-separated structure is prepared as follows:
providing a substrate, and forming at least a two-phase structure on the surface of the substrate, wherein the two-phase structure comprises a first phase structure and a second phase structure which can be separated.
Preferably, a GaN film is formed on the surface of the substrate by using a GaN film growth technology, the GaN film has the first phase structure and the second phase structure, the first phase structure is a GaN crystal phase, the second phase structure is a gallium liquid phase, and the GaN film is etched to remove the gallium liquid phase to form the porous structure.
Preferably, the second phase structure is embedded in the first phase structure, the first phase structure is selected from a GaN film, multiple etching is carried out on the GaN film, and a pore structure is formed by etching part of the GaN film to obtain the porous structure.
Preferably, the second phase structure comprises second quantum dots, and the parts of the second phase structure except the second quantum dots are corroded, and the second quantum dots are remained in the porous structure.
Preferably, the second quantum dot is at least one selected from the group consisting of GaAs quantum dot, InP quantum dot, CdS quantum dot, CdSe quantum dot, CdTe quantum dot, ZnSe quantum dot, PbS quantum dot, PbSe quantum dot, InAs quantum dot, InGaN quantum dot.
Preferably, the first phase structure contains first quantum dots, the second phase structure contains second quantum dots, and the portion of the second phase structure other than the second quantum dots is etched, and the second quantum dots are retained in the porous structure.
Preferably, an epitaxial film is formed on the surface of the substrate by using a GaN film growth technology and a Ga source, an As source and an N source, a GaN film embedded with GaAs quantum dots is formed by an epitaxial process or an annealing process, the GaN film is corroded to form the porous structure, and the porous structure contains the GaAs quantum dots.
Preferably, an InGaN thin film with a high In content is prepared on the surface of the substrate, the InGaN thin film with the high In content spontaneously generates component phase separation to form the first phase structure and the second phase structure, and the first phase structure is low InyGa1-yAn N phase, the second phase structure being In-rich InxGa1-xN phase, x>>y, the first phase structure and the second phase structure are embedded in the thin film in a mode of crystal grains with different sizes in space,
etching the second phase structure to form the porous structure, wherein the porous structure does not contain or contains In rich InxGa1-xAnd (4) N quantum dots.
Correspondingly, the invention also provides a color conversion layer prepared by the preparation method.
Compared with the prior art, the invention provides a preparation method of a color conversion layer, which comprises the steps of providing a phase separation structure, corroding the phase separation structure to form a porous structure, filling first quantum dots in the porous structure, realizing enhancement of light with the same color if the first quantum dots with the same size are filled, and matching light with different colors if two or more than two first quantum dots are filled.
Drawings
FIG. 1 shows a schematic structural diagram of a phase separation structure in embodiment 2 of a color conversion layer according to the invention.
Fig. 2 shows a schematic diagram of the phase-separated structure of fig. 1 after etching to form a porous structure.
Fig. 3 shows a schematic structural diagram of quantum dots filled in the porous structure in fig. 2.
FIG. 4 shows a schematic structural diagram of a phase separation structure in embodiment 3 of the color conversion layer according to the invention.
Fig. 5 shows a schematic diagram of the phase-separated structure of fig. 4 after etching to form a porous structure.
Fig. 6 shows a schematic structure diagram of quantum dots filled in the porous structure in fig. 5.
FIG. 7 shows a schematic structure diagram of an electrical excitation application in embodiment 5 of the color conversion layer of the present invention.
Description of the symbols:
a substrate 110, an InGaN thin film 120, a first phase structure 121, a second phase structure 122, InyGa1-yN quantum dots 123, InxGa1-xN quantum dots 124, cadmium sulfide quantum dots 125, epitaxial film 130, GaAs quantum dots 131, InP quantum dots 133, GaN film 140, conductive structure 210, and electrode 220.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the present invention in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
The invention provides a preparation method of a color conversion layer, which comprises the following steps:
(1) providing a phase separation structure;
(2) corroding the phase separation structure to make the phase separation structure have a porous structure;
(3) and filling the porous structure with the first quantum dots.
The phase separation structure may be a two-phase separation structure or a multi-phase separation structure, and one of the phases may be removed by etching through a certain technique, such as gas etching, electrochemical etching, and solution etching, but is not limited thereto. After the etching, one of the phase structures may be completely removed, or the quantum dots in the phase structure may be left to fill the portion after the etching. Further, the crystal quality of the phase separation structure is low, and the surface is in a fog shape, so that the phase separation is facilitated. Furthermore, the phase-separated structure is conductive, can be realized by doping, and is electrically n-type or p-type.
The porous structure refers to a phase separation structure in which pores formed by one phase structure are removed or grooves, pits, or holes formed by etching one phase structure are etched. For the latter, the quantum dots in the phase structure can also be retained, but the same appliesThe quantum dots can be removed, preferably with the quantum dots remaining in a porous structure. Furthermore, the corrosion mode can be gas corrosion, electrochemical corrosion, solution corrosion and other technical means. In which the gas corrodes, e.g. H2、HCL。
The filling of the first quantum dots in the porous structure means that at least one kind of the first quantum dots, more preferably 2 or more kinds of the first quantum dots are filled, and if two or more kinds of the first quantum dots with different sizes are filled, light with different colors can be obtained. And quantum dots with the same size can be continuously filled to realize the enhancement of the conversion of light with the same color. Further, the quantum dots may be filled by means of, but not limited to, impregnation and electric field injection. Still further, the first quantum dot is selected from at least one of a cadmium sulfide (CdS) quantum dot, a cadmium selenide (CdSe) quantum dot, a cadmium telluride (CdTe) quantum dot, a zinc selenide (ZnSe) quantum dot, a lead sulfide (PbS) quantum dot, a lead selenide (PbSe) quantum dot, an indium arsenide (InAs) quantum dot, an InGaN quantum dot, a GaAs quantum dot, an InP quantum dot.
Further, providing a substrate, and forming at least a two-phase structure on the surface of the substrate, wherein the two-phase structure comprises a first-phase structure and a second-phase structure which are separated, so that the phase separation structure is obtained. Specifically, in some embodiments, a GaN film is formed on the surface of the substrate by using a GaN film growth technique, the GaN film has a first phase structure and a second phase structure, the first phase structure is a GaN crystal phase, the second phase structure is a gallium liquid phase, and the GaN film is etched to remove the gallium liquid phase to form a porous structure. The GaN film growth technique can adopt, but is not limited to, HVPE or MOCVD technique. More preferably, the surface of the GaN film is a matte surface to facilitate phase separation, and a large number of V-shaped pits are distributed on the surface of the GaN film.
In a preferred embodiment, the second phase structure is embedded in the first phase structure, the first phase structure is selected from a GaN film, the GaN film is subjected to multiple etching, and the etching partially forms a pore structure to obtain a porous structure. In this manner, since the second phase structure is embedded in the first phase structure, the second phase structure can be etched so that the portion forms a hole. More preferably, however, the second phase structure comprises second quantum dots, and removing the portion (e.g., solution) of the second phase structure other than the second quantum dots, without etching the second quantum dots, remains in the porous structure, but does not preclude the second quantum dots from being removed from the porous structure. Preferably, the first phase structure contains first quantum dots, the second phase structure contains second quantum dots, and the etching removes a portion (e.g., solution) of the second phase structure other than the second quantum dots, and the second quantum dots remain in the porous structure. When the quantum dots are formed in the first phase structure in a specific mode, the first phase structure contains the first quantum dots, and the second phase structure contains the second quantum dots, so that light leakage is reduced, and the color conversion effect is enhanced. Still further, the second quantum dot is selected from at least one of GaAs quantum dot, InP quantum dot, cadmium sulfide (CdS) quantum dot, cadmium selenide (CdSe) quantum dot, cadmium telluride (CdTe) quantum dot, zinc selenide (ZnSe) quantum dot, lead sulfide (PbS) quantum dot, lead selenide (PbSe) quantum dot, indium arsenide (InAs) quantum dot, InGaN quantum dot.
It is understood that the manner of forming the first phase structure including the first quantum dots is achieved using GaN film growth techniques in combination with different materials. In one embodiment, an epitaxial film is formed on the surface of a substrate by using a GaN film growth technology and a Ga source, an As source and an N source, a GaN film embedded with GaAs quantum dots is formed by an epitaxial process or an annealing process, and the GaN film is corroded to form a porous structure, wherein the porous structure contains the GaAs quantum dots. In another embodiment, an epitaxial film is formed on the surface of the substrate by using a GaN film growth technology and a Ga source, an In source, a P source and an N source, and then the GaN film embedded with InP quantum dots can be formed through an epitaxial process or an annealing process, and the GaN film is corroded to form a porous structure, wherein the porous structure contains the InP quantum dots.
In a preferred embodiment, an InGaN thin film with high In content is prepared on the surface of a substrate, and the InGaN thin film with high In content spontaneously undergoes composition phase separation to form a first phase structure and a second phase structure, wherein the first phase structure is low InyGa1-yN phase and containing InyGa1-yN quantum dots, the second phase structure is In rich InxGa1-xN phase and InxGa1-xN quantum dots, x>>y, first phase structure andthe two-phase structure is embedded In the film In a mode of crystal grains with different sizes In space, the second-phase structure is corroded to form a porous structure, and the porous structure does not contain or contains In rich InxGa1-xAnd (4) N quantum dots. More preferably, 0.3<x<1,0<y<0.2。
In a preferred embodiment, the color conversion layer of the present invention is disposed on an excitation light source, which is an LED or LD (laser diode), and the quantum dots are excited by the excitation light source to emit light, such as blue light, green light, or UV light. In some embodiments, the color conversion layer of the present invention can be reversed on the conductive structure by electroluminescence, and an electrode is formed on one side of the color conversion layer. The surface of the conductive structure, which is opposite to the color conversion layer, is provided with an electrode, and the surface, which is opposite to the color conversion layer, is made of ITO or a semiconductor material which is opposite to the color conversion layer in electrical property and is made of the same material, so that the quantum dots are electrically excited.
The method for producing the color conversion layer according to the invention is explained in detail below with reference to the attached FIGS. 1 to 7 by means of several specific examples.
Example 1
A method of preparing a color conversion layer, comprising the steps of:
(1) providing a substrate, epitaxially growing a gallium-rich GaN film on the substrate by using an HVPE (high voltage vapor deposition) technology, forming two phases, a GaN crystal phase and a gallium liquid phase on the GaN film, wherein the surface of the GaN film is a matte surface and is distributed with a large number of V-shaped pits (V pits);
(2) removing liquid-phase gallium by using solution corrosion, and then using electrochemistry corrosion to form a V-shaped pit so that the GaN film forms a porous structure;
(3) cadmium sulfide (CdS) quantum dots and indium arsenide (InAs) quantum dots are filled in the porous structure in a leaching mode.
Example 2
Referring to fig. 1-3, a method for preparing a color conversion layer includes the steps of:
(1) providing a substrate 110, epitaxially growing an InGaN thin film 120 with a high In content on the surface of the substrate 110 by HVPE, wherein the InGaN thin film 120 with a high In content spontaneously undergoes composition phase separation due to high In content to form In with low InyGa1-yN phase andin-rich InxGa1-xN phase, first phase structure 121 is In with low InyGa1-yN phase and containing InyGa1-yN quantum dots 123, the second phase structure 122 being In-rich InxGa1-xN phase and containing InxGa1-x N Quantum dots 124, x>>y, x is 0.4, y is 0.02, and the first phase structure 121 and the second phase structure 122 are spatially embedded in the thin film in the form of grains with different sizes, please refer to fig. 1;
(2) using H2Gas etching to remove In-rich InxGa1-xN phase forming a porous structure consisting essentially of the first phase structure 121, the porous structure having In-rich InxGa1-x N Quantum dots 124, the first phase structure 121 itself, containing InyGa1-yN quantum dots 123, please refer to fig. 2;
(3) cadmium sulfide (CdS) quantum dots 125 are filled in the porous structure by means of electric field injection, please refer to fig. 3.
Example 3
Referring to fig. 4-6, a method for preparing a color conversion layer includes the steps of:
(1) providing a substrate 110, introducing a Ga source, an As source and an N source into MOCVD at the same time to form an epitaxial film 130, and forming a GaN film 140 embedded with GaAs quantum dots 131 by an epitaxial process, please refer to fig. 4;
(2) corroding the GaN film 140 by electrochemical corrosion to form a GaN porous structure, wherein GaAs quantum dots 131 are arranged in the porous structure, and the other non-corroded parts are also embedded with the GaAs quantum dots 131, please refer to FIG. 5;
(3) the InP quantum dots 133 are filled in the porous structure by electric field injection, please refer to fig. 6.
Example 4
(1) Providing a substrate, simultaneously introducing a Ga source, an In source, a P source and an N source In MOCVD (metal organic chemical vapor deposition) to form an epitaxial film, and forming a GaN film embedded with InP quantum dots by an epitaxial process;
(2) corroding the GaN film by electrochemical corrosion to form a GaN porous structure, wherein InP quantum dots are arranged in the porous structure, and InP quantum dots are also embedded in the rest un-corroded parts;
(3) and filling cadmium selenide (CdSe) quantum dots in the porous structure in an electric field injection mode.
Example 5
Referring to fig. 7, in an application of the color conversion layer, the color conversion layer obtained in example 2 is flipped over a conductive structure 210, and an electrode 220 is formed on one side of the color conversion layer. The conductive structure 210 has an electrode (not shown) on a side opposite to the color conversion layer, and the side opposite to the color conversion layer is made of ITO or a semiconductor material having an electrical property opposite to that of the color conversion layer.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.

Claims (10)

1. A method of making a color conversion layer, comprising the steps of:
(1) providing a phase separation structure;
(2) corroding the phase separation structure to make the phase separation structure have a porous structure;
(3) and filling the porous structure with first quantum dots.
2. The method for preparing a color conversion layer according to claim 1, wherein in step (1), the phase-separated structure is prepared as follows:
providing a substrate, and forming at least a two-phase structure on the surface of the substrate, wherein the two-phase structure comprises a first phase structure and a second phase structure which can be separated.
3. The method according to claim 2, wherein a GaN film is formed on the surface of the substrate by using a GaN film growth technique, wherein the GaN film has the first phase structure and the second phase structure, the first phase structure is a GaN crystal phase, the second phase structure is a gallium liquid phase, and the GaN film is etched to remove the gallium liquid phase to form the porous structure.
4. The method of preparing a color conversion layer according to claim 2, wherein the second phase structure is embedded in the first phase structure, the first phase structure is selected from a GaN film, the GaN film is etched at a plurality of places, and a pore structure is formed by etching a part of the GaN film to obtain the porous structure.
5. The method of preparing a color conversion layer according to claim 4, wherein the second phase structure comprises second quantum dots, and a portion of the second phase structure other than the second quantum dots is etched, and the second quantum dots remain in the porous structure.
6. The method of preparing a color conversion layer according to claim 5, wherein the second quantum dots are selected from at least one of GaAs quantum dots, InP quantum dots, CdS quantum dots, CdSe quantum dots, CdTe quantum dots, ZnSe quantum dots, PbS quantum dots, PbSe quantum dots, InAs quantum dots, InGaN quantum dots.
7. The method of preparing a color conversion layer according to claim 2, wherein the first phase structure contains first quantum dots, the second phase structure contains second quantum dots, and a portion of the second phase structure other than the second quantum dots is etched, and the second quantum dots remain in the porous structure.
8. The method of manufacturing a color conversion layer according to claim 7, wherein an epitaxial film is formed on the surface of the substrate by using a GaN film growth technique with a Ga source, an As source, and an N source, and then a GaN film embedded with GaAs quantum dots is formed by an epitaxial process or an annealing process, and the GaN film is etched to form the porous structure, wherein the porous structure contains the GaAs quantum dots.
9. The method of preparing a color conversion layer according to claim 2, wherein a high In InGaN thin film is prepared on the surface of the substrate, the high In InGaN thin film spontaneously emittingSeparating raw components to form the first phase structure and the second phase structure, wherein the first phase structure is In low InyGa1-yAn N phase, the second phase structure being In-rich InxGa1-xN phase, x>>y, the first phase structure and the second phase structure are embedded in the film in a grain mode with different sizes in space,
etching the second phase structure to form the porous structure, wherein the porous structure does not contain or contains In rich InxGa1-xAnd (4) N quantum dots.
10. A color conversion layer, characterized in that it is produced by the production method as claimed in any of claims 1 to 9.
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CN114050212A (en) * 2021-11-08 2022-02-15 邬宗秀 Quantum dot light conversion film and preparation method thereof

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