CN117747733A - Ferroelectric film/GaN-based LED integrated red light chip and preparation method thereof - Google Patents
Ferroelectric film/GaN-based LED integrated red light chip and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photoelectron manufacturing, and discloses a ferroelectric film/GaN-based LED integrated red light chip and a preparation method thereof. The chip comprises a substrate from bottom to top; a buffer layer over the substrate; an n-type doped GaN layer positioned above the buffer layer; an active layer over the n-doped GaN layer; a p-type doped electron blocking layer located over the active layer; a p-type doped GaN layer positioned above the p-type doped electron blocking layer; siO (SiO) 2 An insulating layer over the p-type doped layer; ferroelectric thin film layer located at SiO 2 Over the insulating layer. The ferroelectric film adopted by the invention is integrated with the GaN-based LED, and the non-red LED (lambda is 570-600 nm) which is mature in the epitaxial technology is directly converted into the red LED (more than 620 nm) by utilizing the regulation and control effect of ferroelectric polarization, so that the high-quality and high-efficiency red light luminescence is realized.
Description
Technical Field
The invention relates to the technical field of photoelectron manufacturing, in particular to a ferroelectric film/GaN-based LED integrated red light chip and a preparation method thereof.
Background
The GaN-based light emitting diode has wide application prospect in the fields of illumination, display, communication and the like due to the characteristics of high efficiency, high brightness, quick response, long service life, good color purity and the like. At present, in three primary colors GaN-based LEDs, compared with blue-green LEDs, the preparation of GaN-based red LEDs is very difficult, the luminous efficiency is low, and the use requirements of actual production cannot be met. The reason for the inefficiency is that the large lattice and thermal mismatch between the GaN epitaxial layer and the substrate can result in a large number of defects in the epitaxial layer. In addition, the difference of the growth temperatures of the InN material and the GaN material causes that the N equilibrium vapor pressure of InN In a growth state is far greater than that of GaN, so that GaN and InN are difficult to be mutually dissolved, and as the In component In the InGaN material is continuously increased, the phase separation phenomenon of InN caused by the equilibrium vapor pressure becomes more serious, and the luminous efficiency of the LED is further reduced. Currently, in order to improve the luminous efficiency of the red micro-LED, researchers have proposed many schemes including substrate selection, buffer layer design, and the like. But it cannot fundamentally obtain GaN-based red LEDs with high luminous efficiency, high color purity, and high color stability.
Disclosure of Invention
The invention aims to provide a ferroelectric film/GaN-based LED integrated red light chip and a preparation method thereof, which are used for solving the problem that the existing method cannot fundamentally obtain a GaN-based red light LED with high luminous efficiency, high color purity and high color stability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a ferroelectric film/GaN-based LED integrated red light chip, which comprises the following structures:
a substrate;
a buffer layer over the substrate;
the n-type doped GaN layer is positioned above the buffer layer;
an active layer over the n-doped GaN layer;
a p-type doped electron blocking layer located over the active layer;
a p-type doped GaN layer positioned above the p-type doped electron blocking layer;
SiO 2 an insulating layer located above the p-type doped GaN layer;
a ferroelectric thin film layer located on the SiO 2 Over the insulating layer to provide ferroelectric polarization.
Preferably, the material of the substrate is GaN, si, siC or sapphire, and the structure of the substrate comprises a planar substrate and a patterned substrate.
Preferably, the ferroelectric thin film layer comprises PbZrTiO 3 、BiFeO 3 、BaTiO 3 Ferroelectric materials having strong polarization characteristics, including ScAlN; the ferroelectric film layer is deposited by chemical solution deposition or pulse laser deposition; the ferroelectric thin film layer has a polycrystalline or epitaxial structure.
Preferably, the ferroelectric thin film layer has a thickness of 1nm to 1 μm.
Preferably, the epitaxial material of the chip comprises GaN, inGaN or AlGaN.
Preferably, the active layer is a multi-pair InGaN/GaN quantum well structure, and is a light-emitting source of a chip.
Preferably, the n-type doped GaN layer and the p-type doped GaN layer are respectively plated with an n-type electrode and a p-type electrode, the n-type electrode is positioned above the n-type doped GaN layer and forms ohmic contact with the n-type doped GaN layer, and the p-type electrode is positioned above the p-type doped GaN layer and forms ohmic contact with the p-type doped GaN layer.
Preferably, the ferroelectric film/GaN-based LED integrated red light chip is a large-size LED or a mini/micro-LED.
The invention also provides a preparation method of the ferroelectric film/GaN-based LED integrated red light chip, which comprises the following steps:
(1) Sequentially growing a buffer layer, an n-type doped GaN layer, an active layer, a p-type doped electron blocking layer, a p-type doped GaN layer and SiO on a substrate 2 An electron blocking layer, a ferroelectric thin film layer;
(2) A metal mask plate is arranged on the p-type doped GaN layer;
(3) Etching the p-type doped GaN layer, the p-type doped electron blocking layer and the active layer by using the mask plate obtained in the step (2) as a template through an inductive coupling plasma etching technology until the n-type doped GaN layer is reached;
(4) Depositing SiO on the epitaxial wafer etched with the n-doped GaN layer 2 An insulating layer;
(5) In SiO 2 Depositing a ferroelectric film on the insulating layer;
(6) Preparing a p-type electrode in ohmic contact with the p-type doped GaN layer and an n-type electrode in ohmic contact with the n-type doped GaN layer; and obtaining the ferroelectric film/GaN-based LED integrated red light chip.
Preferably, the circular metal mask plate is used for etching the n-type doped GaN layer; the p-type electrode and the n-type electrode are the same in metal lamination, and the structure is Ti/Pt/Au sequentially from bottom to top.
Compared with the prior art, the invention has the following beneficial effects:
(1) Unlike most of the direct growth GaN-based red LEDs by regulating and controlling the In component of the multiple quantum wells, the invention adopts the integration of the ferroelectric film and the GaN-based LEDs to realize high-quality and high-efficiency red light luminescence, and avoids the difficulty of material growth;
(2) The invention uses ferroelectric polarization to regulate and control the energy band structure and carrier recombination process of the GaN-based LED quantum well, thereby realizing the GaN-based red LED with high luminous efficiency, high color purity and high color stability. Provides great reference significance for the preparation of novel electrical devices;
(3) The ferroelectric film of the invention is compatible with the current semiconductor chip technology, does not influence the chip preparation technology, and can realize large-scale production;
(4) The present invention is relatively easy in view of the ferroelectric thin film growth process. Different growth processes can be selected to realize the preparation of polycrystal or epitaxy of the ferroelectric film. The luminous wavelength and the color coordinates of the LED are precisely controlled by adjusting parameters such as thickness, composition, polarization direction and the like of the ferroelectric material. Therefore, the chip capable of emitting red light can be obtained, and the quantum efficiency and the photoelectric conversion efficiency of the chip can be flexibly improved;
(5) The high-efficiency GaN-based red light LED prepared by the invention can be used for preparing mini/micro-LEDs and is used for RGB three-color integrated display arrays, so that full-color display of total nitrogen is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a structural elevation view of a ferroelectric thin film/GaN-based LED integrated red light chip of an embodiment;
FIG. 2 is a structural side view of a ferroelectric thin film/GaN-based LED integrated red light chip of an embodiment;
FIG. 3 is a top view of a ferroelectric thin film/GaN-based LED integrated red light chip of an embodiment;
FIG. 4 is a block diagram of materials obtained in each step in the method for fabricating a ferroelectric thin film/GaN-based LED integrated red light chip according to an embodiment;
in FIGS. 1-4, 1-substrate; 2-a buffer layer; a 3-n type doped GaN layer; 4-an active layer; electron blocking of the 5-p type doping; a 6-p type doped GaN layer; 7-SiO 2 A barrier layer; 8-a ferroelectric thin film layer; a 9-n type electrode; 10-p type electrode.
Detailed Description
The invention aims to integrate a red light chip by a ferroelectric film/GaN-based LED based on ferroelectric polarization regulation effect, and simultaneously provides a preparation method thereof, wherein the ferroelectric film is deposited on a GaN-based LED epitaxial wafer (lambda is 570-600 nm) which is relatively mature in epitaxial technology, the energy band structure and carrier recombination process of a GaN-based LED quantum well are regulated by ferroelectric polarization, so that the growth of the light wavelength of the GaN-based LED is realized, the high-quality and high-efficiency red light emission (lambda is more than 620 nm) is obtained, and the difficulty of directly growing the GaN-based red light LED is avoided.
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
As one aspect of the present invention, there is provided a ferroelectric thin film/GaN-based LED integrated red light chip comprising:
a substrate;
a buffer layer over the substrate;
the n-type doped GaN layer is positioned above the buffer layer;
an active layer over the n-doped GaN layer;
a p-type doped electron blocking layer located over the active layer;
a p-type doped GaN layer positioned above the p-type doped electron blocking layer;
SiO 2 an insulating layer located above the p-type doped GaN layer;
a ferroelectric thin film layer located on the SiO 2 Over the insulating layer to provide ferroelectric polarization.
In an embodiment of the invention, the substrate material comprises GaN, si, siC or sapphire, the structure of which comprises a planar substrate and a patterned substrate;
in an embodiment of the present invention, the epitaxial material includes GaN, inGaN, and AlGaN;
in an embodiment of the present invention, the active layer is multicycle In x Ga 1-x N/GaN structure, in is changed by regulating In component x Ga 1-x Forbidden band width E of N g 。
The light-emitting wavelength of the GaN-based LED epitaxial wafer grown in the embodiment of the invention is 570-600nm;
in an embodiment of the invention, siO 2 The insulating layer can be selected to have different deposition thicknesses or not;
in an embodiment of the invention, the ferroelectric thin film is a ferroelectric material with strong polarization characteristics, including PbZrTiO 3 ，BiFeO 3 ，BaTiO 3 ScAlN, etc.;
in an embodiment of the present invention, the ferroelectric thin film deposition method includes Chemical Solution Deposition (CSD), pulsed Laser Deposition (PLD), and the like;
in an embodiment of the present invention, the ferroelectric thin film may be a polycrystalline thin film or an epitaxial thin film;
in an embodiment of the present invention, the integrated red light chip may further include an ITO layer, which is located between the ferroelectric thin film and the electrode, and is made of In 2 O 3 And SnO 2 ；
In an embodiment of the invention, the integrated red light chip further comprises a p-type electrode and an n-type electrode, which form ohmic contacts with the p-type doped GaN and the n-type doped GaN, respectively.
In the embodiment of the invention, the integrated red light chip can be prepared into a mini-LED or a micro-LED according to different manufacturing processes.
As an aspect of the present invention, there is also provided a method for manufacturing a ferroelectric thin film/GaN-based LED integrated red light chip, comprising the steps of:
(1) Sequentially growing a buffer layer, an n-type doped GaN layer, an active layer, a p-type doped electron blocking layer, a p-type doped GaN layer and SiO on a substrate 2 An insulating layer and a ferroelectric thin film layer;
(2) A metal mask plate is arranged on the p-type doped GaN layer;
(3) Etching the p-type doped GaN layer, the p-type doped electron blocking layer and the active layer by using the mask plate obtained in the step (2) as a template through an inductive coupling plasma etching technology until the n-type doped GaN layer is reached;
(4) Depositing SiO on the epitaxial wafer etched with the n-doped GaN layer 2 An insulating layer deposited to a thickness of hundreds of nanometers;
(5) In SiO 2 Depositing a ferroelectric thin film on the insulating layer, wherein the thickness of the ferroelectric thin film can be tens of nanometers to hundreds of nanometers;
(6) Preparing a p-type electrode in ohmic contact with the p-type doped GaN layer and an n-type electrode in ohmic contact with the n-type doped GaN layer; and obtaining the ferroelectric film/GaN-based LED integrated red light chip.
In embodiments of the present invention, the ferroelectric thin film layer thickness may be from tens of nanometers to hundreds of nanometers. The size of the integrated red light chip may vary from hundreds of microns to tens of microns depending on the process.
The following further explains the technical solution of the present invention according to the specific embodiment, and it should be noted that this embodiment is only used to explain the technical solution of the present invention, but the present invention is not limited thereto.
Referring to fig. 1 to 4, the present invention provides a ferroelectric thin film/GaN-based LED integrated red light chip, comprising:
a substrate 1, the material of the substrate 1 in this embodiment being sapphire, which is a PSS patterned substrate;
a buffer layer 2 located above the substrate 1, wherein the buffer layer 2 is composed of an AlN nucleation layer and unintentionally doped u-GaN, a layer of AlN film is firstly grown on the PSS patterned substrate by using a Physical Vapor Deposition (PVD) method, then the unintentionally doped u-GaN is grown by using a metal organic chemical vapor epitaxy (MOCVD) method, and in the process, high-purity ammonia gas is used as a nitrogen source, and trimethyl gallium and triethyl gallium are used as gallium sources;
an n-type doped GaN layer 3 having a doping concentration of about 1×10 and located above the buffer layer 2 18 cm -3 The doping source is silane, high-purity ammonia gas is used as a nitrogen source, and trimethyl gallium and triethyl gallium are used as gallium sources;
the active layer 4 is positioned above the n-type doped GaN layer 3 and consists of a plurality of pairs of InGaN/GaN multi-quantum wells, the InGaN takes high-purity ammonia gas as a nitrogen source, trimethyl indium as an indium source, trimethyl gallium or triethyl gallium as a gallium source to grow at the temperature of 750 ℃, the GaN takes high-purity ammonia gas as a nitrogen source, and trimethyl gallium or triethyl gallium as a gallium source to grow at the temperature of 870 ℃;
the p-type doped electron blocking layer 5 is positioned above the active layer, takes magnesium dipentahydrate as a doping source at 900 ℃, takes high-purity ammonia gas as a nitrogen source, and trimethylaluminum as an aluminum source, and trimethylgallium or triethylgallium as a gallium source to grow into p-AlGaN;
the p-type doped GaN layer 6 is positioned above the p-type doped electron blocking layer 5, the p-type doped GaN layer 6 takes magnesium dipentahydrate as a doping source, high-purity ammonia gas as a nitrogen source, trimethyl gallium or triethyl gallium as a gallium source is grown at the temperature of 940 ℃, and the doping concentration is about 1 multiplied by 10 20 cm -3 ；
SiO 2 An electron blocking layer 7, having a thickness of several hundred nanometers, is located over the p-type doped GaN layer 6.
Ferroelectric thin film layer 8, located at SiO 2 Above the electron blocking layer 7 is a ferroelectric material with strong polarization properties, including BiFeO 3 、PrZrTiO 3 、BaTiO 3 Ferroelectric materials such as Scan. The preparation method comprises chemical solution deposition, pulse laser deposition and other methods. The flow of preparing the ferroelectric film by the CSD method is as follows: first preparing a precursor solution, and then coating the precursor solution outside the GaN-based LED by using a spin coating modeThe ferroelectric thin films (n layers) with different layers, namely the thickness between tens and hundreds of nanometers, are coated on the extension piece. Finally, the wet film is subjected to heat treatment, wherein the annealing temperature is 550-700 ℃ and the annealing time is 30min. The PLD method for preparing the ferroelectric film comprises the following steps: firstly, preparing a required target material, then selecting proper growth parameters such as growth temperature, cavity oxygen partial pressure, laser energy density and the like, and finally depositing an epitaxial film.
An electrode, an ohmic-contact n-type electrode 9 is plated on the n-type doped GaN layer 3, and an ohmic-contact n-type electrode 10 is plated on the ferroelectric thin film layer 8 on the p-type doped GaN layer 6.
Referring to fig. 4, and referring to fig. 1, 2 and 3, the invention provides a method for preparing a ferroelectric thin film/GaN-based LED integrated red light chip, comprising the following steps:
step 1: a buffer layer 2, an n-type doped GaN layer 3, an active layer 4, a p-type doped electron blocking layer 5 and a p-type doped GaN layer 6 are sequentially grown on a substrate 1, and a multicycle In is grown alternately and periodically x Ga 1-x N/GaN structure, in is changed by regulating In component x Ga 1-x Forbidden band width E of N g Thereby regulating and controlling the light-emitting wavelength of the LED, wherein the light-emitting wavelength of the grown GaN-based LED epitaxial wafer is 570-600nm; as shown in fig. 4 (a);
wherein the substrate material is sapphire and the substrate material is silicon,
step 2: and (3) etching the GaN epitaxial wafer obtained in the step (1) by using an inductively coupled plasma etching technology and taking the photoresist pattern as a mask, wherein an etching part sequentially comprises a p-type doped GaN layer 6, a p-type doped electron blocking layer 5 and an active layer 4 from top to bottom until the etching part is etched above the n-type doped GaN layer 3. After etching is completed, siO is deposited by CVD method 2 An insulating layer 7 as shown in fig. 4 (b);
step 3: the ferroelectric thin film 8 is deposited using a Chemical Solution Deposition (CSD) method. The flow is as follows: firstly preparing a precursor solution, and then coating ferroelectric films with different layers, namely, thicknesses between tens and hundreds of nanometers, on a GaN-based LED epitaxial wafer by using a spin coating mode. Finally, the wet film was heat treated at 550℃for 30min. As shown in fig. 4 (c).
Step 4: spin-coating photoresist on the chip obtained in the step 3, wherein the photoresist is negative photoresist, and a pattern is defined by using a photoetching technology through a photoetching plate shown in fig. 4 (d);
step 5: developing the chip obtained in the step 4 in a developing solution to expose the p region and the n region, as shown in fig. 4 (e);
step 6: and (3) evaporating a metal electrode on the chip obtained in the step (5), wherein the metal electrode comprises a p-type electrode and an n-type electrode, the metal lamination used by the p-type electrode and the n-type electrode is the same, the structure is Ti/Pt/Au from bottom to top, metals above the p region and the n region are stripped by utilizing a blue film, and finally, residual photoresist is removed, so that the ferroelectric film/GaN-based LED integrated red light chip is obtained, and the ferroelectric film/GaN-based LED integrated red light chip is shown in fig. 4 (f).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The ferroelectric film/GaN-based LED integrated red light chip is characterized by comprising the following structures:
a substrate;
a buffer layer over the substrate;
the n-type doped GaN layer is positioned above the buffer layer;
an active layer over the n-doped GaN layer;
a p-type doped electron blocking layer located over the active layer;
a p-type doped GaN layer positioned above the p-type doped electron blocking layer;
SiO 2 an insulating layer located above the p-type doped GaN layer;
a ferroelectric thin film layer located on the SiO 2 Over the insulating layer to provide ferroelectric polarization.
2. The ferroelectric thin film/GaN based LED integrated red light chip of claim 1, wherein the substrate is GaN, si, siC or sapphire, and the structure of the substrate comprises a planar substrate and a patterned substrate.
3. The ferroelectric thin film/GaN based LED integrated red light chip of claim 2, wherein the ferroelectric thin film layer comprises PbZrTiO 3 、BiFeO 3 、BaTiO 3 Ferroelectric materials having strong polarization characteristics, including ScAlN; the ferroelectric film layer is deposited by chemical solution deposition or pulse laser deposition; the ferroelectric thin film layer has a polycrystalline or epitaxial structure.
4. A ferroelectric thin film/GaN based LED integrated red light chip as claimed in any one of claims 1 to 3, wherein the ferroelectric thin film layer has a thickness of 1nm to 1 μm.
5. The ferroelectric thin film/GaN based LED integrated red light chip of claim 4, wherein the epitaxial material of the chip comprises GaN, inGaN, or AlGaN.
6. The ferroelectric thin film/GaN based LED integrated red light chip of claim 5, wherein the active layer is a multi-pair InGaN/GaN quantum well structure, which is a light emitting source of the chip.
7. The ferroelectric thin film/GaN-based LED integrated red light chip of claim 6, wherein the n-type doped GaN layer and the p-type doped GaN layer are respectively plated with an n-type electrode and a p-type electrode, the n-type electrode is located above the n-type doped GaN layer and forms ohmic contact with the n-type doped GaN layer, and the p-type electrode is located above the p-type doped GaN layer and forms ohmic contact with the p-type doped GaN layer.
8. The ferroelectric thin film/GaN based LED integrated red light chip of claim 6 or 7, wherein the ferroelectric thin film/GaN based LED integrated red light chip is a large size LED or a mini/micro-LED.
9. The method for manufacturing the ferroelectric thin film/GaN-based LED integrated red light chip as claimed in any one of claims 1 to 8, comprising the steps of:
(1) Sequentially growing a buffer layer, an n-type doped GaN layer, an active layer, a p-type doped electron blocking layer, a p-type doped GaN layer and SiO on a substrate 2 An electron blocking layer, a ferroelectric thin film layer;
(2) A metal mask plate is arranged on the p-type doped GaN layer;
(3) Etching the p-type doped GaN layer, the p-type doped electron blocking layer and the active layer by using the mask plate obtained in the step (2) as a template through an inductive coupling plasma etching technology until the n-type doped GaN layer is reached;
(4) Depositing SiO on the epitaxial wafer etched with the n-doped GaN layer 2 An insulating layer;
(5) In SiO 2 Depositing a ferroelectric film on the insulating layer;
(6) Preparing a p-type electrode in ohmic contact with the p-type doped GaN layer and an n-type electrode in ohmic contact with the n-type doped GaN layer; and obtaining the ferroelectric film/GaN-based LED integrated red light chip.
10. The method for manufacturing the ferroelectric thin film/GaN-based LED integrated red light chip according to claim 9, wherein the circular metal mask is used for etching the n-type doped GaN layer; the p-type electrode and the n-type electrode are the same in metal lamination, and the structure is Ti/Pt/Au sequentially from bottom to top.
Priority Applications (1)
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