CN114076739A - RCLED-based sensor and manufacturing method thereof - Google Patents

RCLED-based sensor and manufacturing method thereof Download PDF

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CN114076739A
CN114076739A CN202010849279.6A CN202010849279A CN114076739A CN 114076739 A CN114076739 A CN 114076739A CN 202010849279 A CN202010849279 A CN 202010849279A CN 114076739 A CN114076739 A CN 114076739A
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layer
metal
rcled
micro
resonant cavity
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CN114076739B (en
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刘文杰
刘怡俊
卓青霞
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Guangdong University of Technology
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Guangdong University of Technology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N2021/258—Surface plasmon spectroscopy, e.g. micro- or nanoparticles in suspension
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The application discloses sensor and manufacturing method based on RCLED, through placing the micro-nano structure array of metal hole array in the emitting diode surface that has the resonant cavity, emitting diode sends out light through the resonant cavity mode selection effect, forms the chamber mould that has higher Q value, simultaneously, the chamber mould of higher Q value and micro-nano structure array interact, need through external light source drive work, just can directly be used for surveying the small change of metal nano hole array surrounding refractive index to can realize convenient bore hole observation.

Description

RCLED-based sensor and manufacturing method thereof
Technical Field
The application relates to the technical field of sensors, in particular to a sensor based on RCLED.
Background
With the development of micro-nano structure technology, the micro-nano structure based surface plasmon resonance receives wide attention, because the surface plasmon can localize light on the surface of the metal micro-nano structure, the field on the metal surface is greatly enhanced. By utilizing such characteristics, a small change in local refractive index can be detected, and in recent years, surface plasmon resonance sensors have been mainly used in the fields of drug screening, disease diagnosis, environmental detection, and the like.
With the increasing demand of instant detection and personal disease diagnosis, a new generation of sensors is required to have the characteristics of high sensitivity, miniaturization, low price, rapid detection and the like, while the traditional sensors are generally based on metal thin film and prism coupling equipment, and have the defects of complicated equipment, high cost and poor portability.
In order to overcome the above problems, researchers have proposed refractive index sensors based on localized plasmon resonance, for example based on metal particles or arrays thereof, but it is generally difficult to achieve miniaturized integrated sensors by means of an external light source.
Disclosure of Invention
The application provides a sensor based on an RCLED and a manufacturing method thereof, which are used for solving the technical problem that the existing sensor still needs to be driven to work by an external light source.
In view of this, a first aspect of the present application provides an RCLED-based sensor, including a resonant cavity light emitting diode, where a micro-nano structure array is disposed on a surface of the resonant cavity light emitting diode;
the resonant cavity light-emitting diode comprises a substrate, a resonant cavity and a semiconductor epitaxial layer, wherein the resonant cavity and the semiconductor epitaxial layer are arranged above the substrate;
the micro-nano structure array comprises a medium layer and a metal hole array arranged on the medium layer.
Preferably, the sensor based on the RCLED further includes a first metal layer, the semiconductor epitaxial layer is sequentially provided with an n-type conducting layer, an active region and a p-type conducting layer from bottom to top, the first metal layer is in ohmic contact with the n-type conducting layer, the p-type conducting layer is provided with a second metal layer, and the second metal layer is in ohmic contact with the p-type conducting layer.
Preferably, the array period of the micro-nano structure array is 300-800nm, the radius of metal holes in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160 nm.
Preferably, the resonant cavity is composed of two reflectors which are correspondingly arranged up and down, wherein the reflectivity of the reflector which is close to the substrate is greater than the reflectivity of the reflector which is far from the substrate.
Preferably, the mirror is one or both of a metal mirror and a distributed lagrange mirror.
Preferably, the dielectric layer is made of silicon nitride, silicon oxide, ITO or other oxide or other nitride dielectric materials.
Preferably, the first metal layer and the second metal layer are made of one or an alloy of gold, silver, aluminum, copper, platinum, palladium and magnesium.
In another aspect, an embodiment of the present application further provides a method for manufacturing an RCLED-based sensor, including the following steps:
s101: forming a resonant cavity on a substrate;
s102: forming a semiconductor epitaxial layer in the resonant cavity, specifically forming an n-type conducting layer, an active region and a p-type conducting layer in the resonant cavity from bottom to top in sequence;
s103: forming a first metal layer on the substrate or the n-type conducting layer, wherein the first metal layer and the n-type conducting layer conduct electricity;
s104: forming a second metal layer on the p-type conducting layer, wherein the second metal layer is in ohmic contact with the p-type conducting layer;
s105: and forming a micro-nano structure array on the resonant cavity, wherein the micro-nano structure array comprises a dielectric layer and a metal hole array arranged on the dielectric layer.
Preferably, the resonant cavity is composed of two reflectors which are correspondingly arranged up and down, wherein the reflectivity of the reflector which is close to the substrate is greater than the reflectivity of the reflector which is far from the substrate.
Preferably, the micro-nano structure array in step S105 is manufactured by an electron beam lithography process or a focused ion beam etching process, an array period of the micro-nano structure array is 300 to 800nm, a radius of a metal hole in the metal hole array is 60 to 300nm, and a metal thickness of the micro-nano structure array is 20 to 160 nm.
According to the technical scheme, the embodiment of the application has the following advantages:
the embodiment of the application provides a sensor based on RCLED and a manufacturing method, a micro-nano structure array of a metal hole array is arranged on the surface of a light emitting diode (RCLED) with a resonant cavity, the light emitting diode emits light to form a cavity mode with a higher Q value through the mode selection effect of the resonant cavity, meanwhile, the cavity mode with the higher Q value and the micro-nano structure array interact with each other, the micro-change of the refractive index around the metal nano hole array can be directly detected through the driving work of an external light source, and therefore convenient naked eye observation can be achieved.
Drawings
FIG. 1 is a flow chart of a method of manufacturing an RCLED-based sensor according to one embodiment of the present application;
FIG. 2 is a flow chart of a method of manufacturing an RCLED-based sensor according to another embodiment of the present application;
fig. 3 is a cross-sectional view of a sample of step S301 in an example one of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 4 is a cross-sectional view of a sample of step S302 in an example one of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 5 is a cross-sectional view of a sample of step S303 in an example one of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 6 is a cross-sectional view of a sample of step S304 in an example one of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 7 is a cross-sectional view of a sample of step S306 in an example one of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 8 is a top view of a sample of step S307 of an example one of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
FIG. 9 is a graph of an infrared spectrum of a sensor having a resonant wavelength of 650nm in an example one of methods of manufacturing an RCLED based sensor according to embodiments of the present application;
fig. 10 is a cross-sectional view of a sample of example two of a method of manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 11 is an infrared spectrum of a sensor having a resonant wavelength of 570nm in example two of the methods for manufacturing an RCLED-based sensor according to embodiments of the present application.
Detailed Description
In order to make the technical solutions of the present application better understood, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In order to facilitate understanding, the sensor based on the RCLED provided by this embodiment includes a resonant cavity light emitting diode, where a micro-nano structure array is disposed on a surface of the resonant cavity light emitting diode;
the resonant cavity light-emitting diode comprises a substrate, a resonant cavity and a semiconductor epitaxial layer, wherein the resonant cavity and the semiconductor epitaxial layer are arranged above the substrate;
the micro-nano structure array comprises a medium layer and a metal hole array arranged on the medium layer.
It should be noted that the dielectric layer can play a supporting role, and a stable metal hole array can be prepared on the dielectric layer. In addition, the dielectric layer can be patterned to form a patterned dielectric layer, the shape of the patterned dielectric layer is the same as that of the metal hole array, and the array is a square or hexagonal hole array.
In addition, the reasonably designed periodic structure can inhibit radiation loss and realize the diversity of coupling between metal modes, but the detuning is caused by overlarge period, the surface plasma resonance coupling effect between holes is weakened, and even the mutual influence can be ignored, and preferably, the array period is 300-800 nm.
Meanwhile, in a certain range, the smaller the aperture of the metal hole is, the lower the generated surface plasmon resonance coupling is, and preferably, the radius is 60-300 nm; the larger the thickness of the metal in the metal micro-nano structure array is, the lower the transmission intensity of incident light is, and preferably, the thickness of the metal in the metal micro-nano structure array is 20-160 nm.
In addition, in this embodiment, the micro-nano structure array of the metal hole array is placed on the surface of a light emitting diode (RCLED) having a resonant cavity, light emitted by the light emitting diode is subjected to a mode selection effect of the resonant cavity to form a cavity mode with a higher Q value, and meanwhile, the cavity mode with the higher Q value interacts with the micro-nano structure array, and can be directly used for detecting a small change in refractive index around the metal nano hole array by driving with an external light source, so that convenient and fast naked eye observation can be realized.
The foregoing is one embodiment of an RCLED-based sensor provided herein, and the following is another embodiment of an RCLED-based sensor provided herein and described in detail.
The sensor based on the RCLED comprises a resonant cavity light-emitting diode, wherein a micro-nano structure array is arranged on the surface of the resonant cavity light-emitting diode;
the resonant cavity light-emitting diode comprises a substrate, a resonant cavity and a semiconductor epitaxial layer, wherein the resonant cavity and the semiconductor epitaxial layer are arranged above the substrate;
the micro-nano structure array comprises a medium layer and a metal hole array arranged on the medium layer.
It should be noted that the dielectric layer can play a supporting role, and a stable metal hole array can be prepared on the dielectric layer. In addition, the dielectric layer can be patterned to form a patterned dielectric layer, the shape of the patterned dielectric layer is the same as that of the metal hole array, and the array is a square or hexagonal hole array.
Furthermore, the sensor based on the RCLED also comprises a first metal layer, wherein the semiconductor epitaxial layer is sequentially provided with an n-type conducting layer, an active region and a p-type conducting layer from bottom to top, the first metal layer is in ohmic contact with the n-type conducting layer, the p-type conducting layer is provided with a second metal layer, and the second metal layer is in ohmic contact with the p-type conducting layer.
Further, the active region includes quantum wells or quantum dots.
Furthermore, the array period of the micro-nano structure array is 300-800nm, the radius of metal holes in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160 nm.
It should be noted that the reasonably designed periodic structure can suppress radiation loss and realize diversity of coupling between metal modes, but if the array period is too large and causes detuning, the surface plasmon resonance coupling effect between metal holes will be weakened, and even the mutual influence can be ignored, preferably, the array period is 300-.
In addition, in a certain range, the smaller the aperture of the metal hole is, the lower the generated surface plasmon resonance coupling is, and the larger the thickness of the metal in the metal micro-nano structure array is, the lower the transmission intensity of incident light is, preferably, the most suitable thickness of the metal in the metal micro-nano structure array is 20-160 nm.
Furthermore, the resonant cavity is composed of two reflectors which are correspondingly arranged up and down, wherein the reflectivity of the reflector which is close to the substrate is larger than that of the reflector which is far from the substrate.
It should be noted that the reflectivity of the mirror can be defined by setting the number of stacked layers of the mirror refractive index material, and the mirror uses one or both of a metal mirror and a Distributed Bragg Reflector (DBR), for example, both mirrors are metal mirrors or distributed bragg reflectors or one is a metal mirror and the other is a distributed bragg reflector. Taking a distributed Bragg reflector as an example, the distributed Bragg reflector is a periodic structure formed by two materials a and B with different refractive indexes through alternate arrangement, the optical thickness of each material is 1/4 of the central reflection wavelength, according to λ Bragg being 4nl, where λ Bragg is the central wavelength of the high reflection band of the distributed Bragg reflector, n is the refractive index of the material, and l is the optical thickness of each material, and then the specific central reflection wavelength can be generated by setting the materials with different refractive indexes and the optical thickness of each material.
Further, the dielectric layer is made of silicon nitride, silicon oxide, ITO or other oxide or other nitride dielectric materials.
Furthermore, the first metal layer and the second metal layer are made of one of gold, silver, aluminum, copper, platinum, palladium and magnesium or alloy.
It should be noted that the principle of the present embodiment is as follows:
(1) this embodiment selects RCLED by selecting RCLED, wherein, the resonant cavity in RCLED has two functions: firstly, optical feedback capacity is provided to form a strong luminescence spectrum, and the light extraction efficiency of specific wavelength is improved, so that the excitation efficiency of surface plasmon is improved; secondly, a mode selection effect is formed, a high-Q-value luminous spectrum is obtained, and the luminous spectrum has larger light intensity change under the same sensitivity, so that naked eye observation is facilitated; meanwhile, a specific central wavelength is set by utilizing the refractive index and the thickness of a reflector stacked dielectric layer, the central wavelength can be 300-1200 nm generally, and when the peak wavelength generated by the resonant cavity light emitting diode is matched with the resonance wavelength of the micro-nano structure, the RCLED has the strongest transmission light intensity through the micro-nano structure; and when the wavelength is detuned, the transmitted light intensity decreases. According to the surface plasmon characteristics, the change of the surface plasmon resonance wavelength is influenced by the change of the refractive index around the metal structure, so that the matching degree of the RCLED peak wavelength and the micro-nano array resonance wavelength can be adjusted, and the light intensity can be adjusted. Therefore, in the structure, the light intensity of the RCLED light transmitted by the micro-nano structure changes along with the refractive index of the surrounding medium. After the corresponding refractive index and the light intensity are calibrated, the refractive index of the detected object can be known through the light intensity change, and the optical fiber can be applied to the aspects of biosensors through similar principles.
(2) In the resonant cavity light-emitting diode based on the semiconductor, a strong resonance electric field is generated on the surfaces of the dielectric layer and the metal structure, and an enhanced electric field is generated on the surface of the metal through energy transportation of the nano round holes. Through the specially designed resonant cavity mode and the periodic micro-nano structure hole array of the embodiment, the array period of the periodic micro-nano structure hole array, the radius of the metal hole and the thickness of the metal film are specifically limited, and surface plasma resonance with specific wavelength can be generated on the surface of the micro-nano metal hole array.
(3) This embodiment compares with ordinary LED through chooseing RCLED for use, because ordinary LED spontaneous radiant light does not pass through resonant cavity modulation effect, the spectrum of produced light is gaussian distribution, when using as the sensor, light and the micro-nano array structure interact of metal, though have the effect that peak wavelength removed, nevertheless because the spectral line width is very wide, its light intensity change is compared little a lot with RCLED under the same sensitivity, consequently, utilize ordinary LED can make the naked eye observe whole effect worse. The resonant cavity in the RCLED has a wavelength selection function, and the intensity, monochromaticity and polarization characteristic of light corresponding to specific wavelength are improved, so that the RCLED is more suitable for excitation of surface plasmons. The metal micro-nano structure can be excited to generate surface plasmon resonance by utilizing the specifically selected light. In addition, RCLEDs have lower radiation losses at a particular wavelength, have a higher quality factor, and are more sensitive to detect small changes.
The foregoing is another embodiment of an RCLED-based sensor provided herein, and the following is an embodiment of a method of manufacturing an RCLED-based sensor provided herein.
For convenience of understanding, referring to fig. 1, the present embodiment provides a method for manufacturing an RCLED-based sensor, including the following steps:
s101: forming a resonant cavity on a substrate;
note that the substrate may be a sapphire substrate, a SiC substrate, a Si substrate, a GaAs substrate, or a quartz substrate.
S102: forming a semiconductor epitaxial layer in the resonant cavity, specifically forming an n-type conducting layer, an active region and a p-type conducting layer in the resonant cavity from bottom to top in sequence;
s103: forming a first metal layer on the substrate or the n-type conducting layer, wherein the first metal layer and the n-type conducting layer are electrically conducted;
when the first metal layer is formed on the substrate, ohmic contact is formed between the first metal layer and the substrate, and the substrate can be an n-type conductive layer or can be conductive through the substrate and the n-type conductive layer; when the first metal layer is formed on the n-type conductive layer, ohmic contact between the first metal layer and the n-type conductive layer is performed, and an annealing process may be used to reduce contact resistance between the first metal layer and the n-type conductive layer.
S104: forming a second metal layer on the p-type conducting layer, wherein the second metal layer is in ohmic contact with the p-type conducting layer;
it should be noted that, the ohmic contact between the second metal layer and the p-type conductive layer may be reduced by an annealing process, and the materials of the first metal layer and the second metal layer may be one of gold, silver, aluminum, copper, platinum, palladium, and magnesium or an alloy.
S105: and forming a micro-nano structure array on the resonant cavity, wherein the micro-nano structure array comprises a dielectric layer and a metal hole array arranged on the dielectric layer.
It should be noted that the dielectric layer is silicon nitride, silicon oxide, ITO or other oxide or nitride dielectric materials, and the dielectric layer plays a supporting role, so that a stable metal hole array can be prepared on the dielectric layer. In addition, the dielectric layer can be patterned to form a patterned dielectric layer, the shape of the patterned dielectric layer is the same as that of the metal hole array, and the array is a square or hexagonal hole array.
The reasonably designed periodic structure can inhibit radiation loss and realize the diversity of coupling among metal modes, but the detuning is caused by overlarge period, the surface plasma resonance coupling effect among metal holes is weakened, and even the mutual influence can be ignored, and preferably, the array period is 300-.
In a certain range, the smaller the aperture of the metal hole is, the lower the generated surface plasmon resonance coupling is, and the larger the thickness of the metal in the metal micro-nano structure array is, the lower the transmission intensity of incident light is, preferably, the thickness of the metal in the metal micro-nano structure array is 20-160 nm.
The foregoing is one embodiment of a method for manufacturing an RCLED-based sensor provided by the present application, and the following is another embodiment of a method for manufacturing an RCLED-based sensor provided by the present application.
Referring to fig. 2, a method for manufacturing an RCLED-based sensor according to this embodiment includes the following steps:
s201: forming a resonant cavity on a substrate, wherein the resonant cavity consists of two reflectors which are correspondingly arranged up and down, and the reflectivity of the reflector which is close to the substrate is greater than that of the reflector which is far from the substrate;
note that the substrate may be a sapphire substrate, a SiC substrate, a Si substrate, a GaAs substrate, or a quartz substrate.
In addition, the reflectivity of the mirror can be defined by setting the number of stacked layers of mirror refractive index material, and the mirror employs one or both of a metal mirror and a Distributed Bragg Reflector (DBR), for example, both mirrors are metal mirrors or distributed bragg reflectors or one is a metal mirror and the other is a distributed bragg reflector. Taking a distributed Bragg reflector as an example, the distributed Bragg reflector is a periodic structure formed by two materials a and B with different refractive indexes through alternate arrangement, the optical thickness of each material is 1/4 of the central reflection wavelength, according to λ Bragg being 4nl, where λ Bragg is the central wavelength of the high reflection band of the distributed Bragg reflector, n is the refractive index of the material, and l is the optical thickness of each material, and then the specific central reflection wavelength can be generated by setting the materials with different refractive indexes and the optical thickness of each material.
S202: forming a semiconductor epitaxial layer in the resonant cavity, specifically forming an n-type conducting layer, an active region and a p-type conducting layer in the resonant cavity from bottom to top in sequence;
s203: forming a first metal layer on the substrate or the n-type conducting layer, wherein the first metal layer and the n-type conducting layer are electrically conducted;
when the first metal layer is formed on the substrate, ohmic contact is formed between the first metal layer and the substrate, and the substrate can be an n-type conductive layer or can be conductive through the substrate and the n-type conductive layer; when the first metal layer is formed on the n-type conductive layer, the first metal layer and the n-type conductive layer are in ohmic contact, and the ohmic contact mode can adopt an annealing process to reduce the contact resistance of the first metal layer and the n-type conductive layer.
S204: forming a second metal layer on the p-type conducting layer, wherein the second metal layer is in ohmic contact with the p-type conducting layer;
it should be noted that, the ohmic contact between the second metal layer and the p-type conductive layer may be reduced by an annealing process, and the materials of the first metal layer and the second metal layer may be one of gold, silver, aluminum, copper, platinum, palladium, and magnesium or an alloy.
S205: the method comprises the steps of manufacturing a micro-nano structure array on a resonant cavity by adopting an electron beam lithography process or a focused ion beam etching process, wherein the micro-nano structure array comprises a dielectric layer and a metal hole array arranged on the dielectric layer, the array period of the micro-nano structure array is 300-800nm, the radius of metal holes in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160 nm.
It should be noted that the dielectric layer is silicon nitride, silicon oxide, ITO or other oxide or nitride dielectric materials, and the dielectric layer plays a supporting role, so that a stable metal hole array can be prepared on the dielectric layer. In addition, the dielectric layer can be patterned to form a patterned dielectric layer, the shape of the patterned dielectric layer is the same as that of the metal hole array, and the array is a square or hexagonal hole array.
In addition, the micro-nano structure array is manufactured by adopting an electron beam lithography process, and the specific steps are that the electron beam lithography technology is controlled by a computer, according to a preset processing pattern, focused electron beams are utilized to expose a resist of a dielectric layer, areas with different dissolving performances are generated in the resist, and according to the dissolving characteristics of the different areas, selective development is utilized to develop, so that a required resist pattern can be obtained; in addition, the specific step of manufacturing the micro-nano structure array by adopting a focused ion beam etching process is to obtain a metal hole array with a preset structure by utilizing focused ion beam etching.
In addition, the reasonably designed periodic structure can inhibit radiation loss and realize the diversity of coupling between metal modes, but the detuning is caused by overlarge period, the surface plasmon resonance coupling effect between metal holes can be weakened, and even the mutual influence can be ignored, and preferably, the array period is 300-800 nm.
In addition, the metal hole array is provided with a plurality of metal holes, the smaller the diameter of the metal holes is in a certain range, the lower the generated surface plasmon resonance coupling is, and the larger the thickness of the metal in the metal micro-nano structure array is, the lower the transmission intensity of incident light is, preferably, the thickness of the metal in the metal micro-nano structure array is 20-160 nm.
Some examples are listed below in connection with the RCLED-based manufacturing method provided by the present application.
Example 1
The example takes a GaAs-based RCLED with the light-emitting center wavelength of 650nm as an example, and provides a manufacturing method of a sensor based on the RCLED, which comprises the following steps:
s301: referring to fig. 3, TiO is provided on an n-type GaAs substrate 11 using a Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE) method2High refractive index layer 12 and MgF2Low refractive index layer 13, TiO2High refractive index layer 12 and MgF2The low refractive index layer 13 is formed by setting the number of material layers to form a bottom distributed bragg reflector 14 with the sum of the number of layers being 60, wherein the central reflection wavelength of the bottom distributed bragg reflector 14 is 650nm, and TiO is set2The high refractive index layer 12 had a refractive index n1 of 2.45, and had a physical thickness of 66.3 nm; MgF2The low refractive index layer 13 had a refractive index n2 of 1.37, and thus had a physical thickness of 118.6 nm;
s302: referring to fig. 4, a Ti/Au metal layer 21 is formed on the back surface of the n-type GaAs substrate 11, polished or not, for ohmic contact with the n-type GaAs substrate 11;
s303: referring to fig. 5, a GaAs-based semiconductor epitaxial layer is formed on the bottom bragg reflector 14, the GaAs-based semiconductor epitaxial layer is sequentially provided with an n-type AlGaAs epitaxial layer 31, a quantum well 32, and a P-type AlGaAs epitaxial layer 33 from bottom to top, and a patterned P-type metal electrode is formed on the P-type AlGaAs epitaxial layer 33;
s304: referring to FIG. 6, TiO is formed on the upper surface of the P-type AlGaAs epitaxial layer 332High refractive index layer 15 and MgF2Low refractive index layer 16, TiO2High refractive index layer 15 and MgF2The low refractive index layer 16 is providedDetermining the number of material layers to form a top distributed LaG reflector 41 with the sum of the number of the material layers being 10;
it should be noted that a resonant cavity is formed between the bottom distributed bragg mirror 14 in step S301 and the top distributed bragg mirror 41 in step S303;
s305: an oxide ITO layer is evaporated on the top distributed Lag reflector 41, and the thickness of the oxide ITO layer is 70 nm;
s306: referring to fig. 7, an Au layer 51 is vapor-plated on the oxide ITO layer, and then a layer of photoresist is coated on the Au layer 51, and electron beam exposure and development are performed to obtain a uniformly arranged polymethyl methacrylate (PMMA) square hole array layer 52, wherein the array period is 0.6um, and the side length of the square hole is 0.1 um;
s307: a reactive ion etching method is adopted to etch a gold film on the polymethyl methacrylate (PMMA) square hole array layer 52 to form a metal hole array, and an oxide ITO layer is correspondingly etched, and finally, an organic solvent is used to remove PMMA to form a micro-nano structure array, please refer to fig. 8, which is a top view of the structure.
Finally, the effect of the RCLED-based sensor formed through the above steps S301 to S307 is simulated, in which the designed structure size corresponds to a resonance wavelength of 650nm, and in order to better quantify the sensing capability of the RCLED-based sensor, a layer of 3nm dielectric film with a refractive index n of 2.3 is coated on the surface of the micro-nano structure array, which is equivalent to a layer of bio-molecular layer adhered on the surface. As shown in fig. 9, by comparing the intensity change of the transmission spectrum of the uncovered and covered dielectric films, the relative intensity change ((0.118458-0.02722)/0.118458 ═ 0.77044) was calculated, whereby it could be judged that the performance of the RCLED-based sensor in the present example was good.
Example two
For convenience of understanding, referring to fig. 10, this example takes a GaN-based semiconductor material with a light emission peak of 570nm as an example, and provides a method for manufacturing an RCLED-based sensor, which includes the following steps:
s401: an AlGaN high refractive index layer 82 and a GaN low refractive index layer 83 are arranged on a sapphire substrate 81 by adopting a Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE) method, the AlGaN high refractive index layer 82 and the GaN low refractive index layer 83 form a bottom distributed Lag reflector 84 with the sum of the number of layers being 40 by setting the number of material layers, wherein the central reflection wavelength of the bottom distributed Lag reflector 84 is 500 nm;
s402: forming a GaN-based semiconductor epitaxial layer on the bottom distributed Lag mirror 84, wherein the GaN-based semiconductor epitaxial layer is sequentially provided with an n-type GaN epitaxial layer 85, a quantum well 87 and a P-type GaN epitaxial layer 88 from bottom to top, an ITO layer is formed on the surface of the P-type GaN epitaxial layer 88, and the ITO layer is in ohmic contact with the P-type GaN epitaxial layer 88;
s403: etching a device unit on the semiconductor epitaxial layer, and exposing the n-type GaN epitaxial layer 85 at two side sections;
s404: forming a Cr/Au layer 86 on the surface of the etched n-type GaN epitaxial layer 85;
s405: formation of TiO on the p-type GaN epitaxial layer 882High refractive index layer 89 and SiO2Low refractive index layer 810, TiO2High refractive index layer 89 and SiO2The low refractive index layer 810 forms a top distributed bragg mirror 811 with a sum of 10 layers by setting the number of material layers;
it should be noted that a resonant cavity is formed between the bottom distributed bragg mirror 84 in step S401 and the top distributed bragg mirror 811 in step S405;
s406: a silicon nitride layer 812 is surface evaporated on top of the top distributed bragg mirror 811, wherein the thickness is 70 nm. An Au layer 813 is evaporated on the surface of the silicon nitride layer 812, and the thickness of the Au layer is 120 nm;
s407: spin-coating PMMA on the surface of the Au layer 813, and carrying out electron beam exposure and development to obtain a PMMA nanopore array with a square hole array pattern, wherein the array period is 0.4um, and the hole radius is 0.1 um;
s408: and sequentially etching the silicon nitride layer 812 and the corresponding etched Au layer 813 by adopting a reactive ion etching method, and removing PMMA by using an organic solvent to form the micro-nano structure array.
Finally, the effect of the RCLED-based sensor formed through the above steps S401 to S408 was simulated, in which the designed structure size corresponds to a resonance wavelength of 570nm, and in order to better quantify the sensing capability of the RCLED-based sensor, a layer of 3nm dielectric film with a refractive index n of 2.3 was coated on the surface of the Au layer 813, which corresponds to the adhesion of a layer of bio-molecular on the surface, and as shown in fig. 11, the relative intensity change ((0.412684-0.218233)/0.412684 of 0.471186) was calculated by comparing the changes in the transmission spectral intensity of the uncoated and coated dielectric films. By the relative intensity result of 0.77044 in example one, which was 0.77044 greater than 0.471186, it is illustrated that the relative intensity change at the resonance wavelength of 650nm is more pronounced in example one, with the sensitivity being higher as the metal nanopore array is longer at the wavelength.
In the several embodiments provided in the present application, it should be understood that the disclosed apparatus and method may be implemented in other ways. For example, the above-described apparatus embodiments are merely illustrative, and for example, the division of the units is only one logical division, and other divisions may be realized in practice, for example, a plurality of units or components may be combined or integrated into another system, or some features may be omitted, or not executed. In addition, the shown or discussed mutual coupling or direct coupling or communication connection may be an indirect coupling or communication connection through some interfaces, devices or units, and may be in an electrical, mechanical or other form.
The units described as separate parts may or may not be physically separate, and parts displayed as units may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the units can be selected according to actual needs to achieve the purpose of the solution of the embodiment.
In addition, functional units in the embodiments of the present application may be integrated into one processing unit, or each unit may exist alone physically, or two or more units are integrated into one unit. The integrated unit can be realized in a form of hardware, and can also be realized in a form of a software functional unit.
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.

Claims (10)

1. A sensor based on RCLED is characterized by comprising a resonant cavity light-emitting diode, wherein a micro-nano structure array is arranged on the surface of the resonant cavity light-emitting diode;
the resonant cavity light-emitting diode comprises a substrate, a resonant cavity and a semiconductor epitaxial layer, wherein the resonant cavity and the semiconductor epitaxial layer are arranged above the substrate;
the micro-nano structure array comprises a medium layer and a metal hole array arranged on the medium layer.
2. The RCLED-based sensor of claim 1, further comprising a first metal layer, wherein the semiconductor epitaxial layer is sequentially provided with an n-type conductive layer, an active region, and a p-type conductive layer from bottom to top, the first metal layer is in ohmic contact with the n-type conductive layer, the p-type conductive layer is provided with a second metal layer, and the second metal layer is in ohmic contact with the p-type conductive layer.
3. The RCLED-based sensor according to claim 1 or 2, wherein the micro-nano structure array has an array period of 300-800nm, the radius of the metal holes in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160 nm.
4. The RCLED-based sensor of claim 1 or 2, wherein the resonant cavity is comprised of two mirrors disposed in an up-down correspondence, wherein the reflectivity of the mirror closer to the substrate is greater than the reflectivity of the mirror further from the substrate.
5. The RCLED-based sensor of claim 4, wherein the reflector employs one or both of a metal reflector and a distributed lagrange reflector.
6. The RCLED-based sensor of claim 1, wherein the dielectric layer is silicon nitride, silicon oxide, ITO, or other oxide or other nitride dielectric material.
7. The RCLED-based sensor of claim 2, wherein the first and second metal layers each comprise one or an alloy of gold, silver, aluminum, copper, platinum, palladium, magnesium.
8. A method of manufacturing an RCLED-based sensor, comprising the steps of:
s101: forming a resonant cavity on a substrate;
s102: forming a semiconductor epitaxial layer in the resonant cavity, specifically forming an n-type conducting layer, an active region and a p-type conducting layer in the resonant cavity from bottom to top in sequence;
s103: forming a first metal layer on the substrate or the n-type conducting layer, wherein the first metal layer and the n-type conducting layer conduct electricity;
s104: forming a second metal layer on the p-type conducting layer, wherein the second metal layer is in ohmic contact with the p-type conducting layer;
s105: and forming a micro-nano structure array on the resonant cavity, wherein the micro-nano structure array comprises a dielectric layer and a metal hole array arranged on the dielectric layer.
9. The RCLED-based sensor of claim 8, wherein the resonant cavity is comprised of two mirrors disposed in an up-down relationship, wherein the reflectivity of the mirror closer to the substrate is greater than the reflectivity of the mirror further from the substrate.
10. The RCLED-based sensor according to claim 8, wherein the micro-nano structure array in step S105 is manufactured by an electron beam lithography process or a focused ion beam etching process, the array period of the micro-nano structure array is 300-800nm, the radius of metal holes in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160 nm.
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