CN114076739B - RCLED-based sensor and manufacturing method thereof - Google Patents

RCLED-based sensor and manufacturing method thereof Download PDF

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CN114076739B
CN114076739B CN202010849279.6A CN202010849279A CN114076739B CN 114076739 B CN114076739 B CN 114076739B CN 202010849279 A CN202010849279 A CN 202010849279A CN 114076739 B CN114076739 B CN 114076739B
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layer
metal
resonant cavity
array
micro
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CN114076739A (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 a sensor based on RCLED and a manufacturing method thereof, wherein a micro-nano structure array of a metal hole array is arranged on the surface of a light emitting diode 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, and meanwhile, the cavity mode with the higher Q value interacts with the micro-nano structure array and can be directly used for detecting the tiny change of refractive index around the metal nano hole array by driving through an external light source, so that the convenient naked eye observation can be realized.

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 RCLEDs.
Background
With the development of micro-nano structure technology, surface plasmon resonance based on micro-nano structure is widely focused, because surface plasmon can localize light on the surface of the metal micro-nano structure, so that the field of the metal surface is greatly enhanced. By utilizing such characteristics, minute changes 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 demands of instant detection and personal disease diagnosis, new generation sensors are required to have the characteristics of high sensitivity, miniaturization, low cost, rapid detection and the like, while traditional sensors are generally based on metal film and prism coupling equipment, and have the disadvantages of complex equipment, high cost and poor portability.
In order to overcome the above problems, researchers have proposed refractive index sensors based on localized plasmon resonance, such as metal particles or arrays thereof, but it is generally difficult to implement miniaturized integrated sensors by external light sources.
Disclosure of Invention
The application provides a sensor based on RCLEDs 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 the above, a first aspect of the present application provides a sensor based on an RCLED, 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, and the semiconductor epitaxial layer is arranged in the resonant cavity;
the micro-nano structure array comprises a dielectric layer and a metal hole array arranged on the dielectric layer.
Preferably, the sensor based on the RCLED further comprises a first metal layer, 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, ohmic contact is performed between the first metal layer and the n-type conductive layer, a second metal layer is arranged on the p-type conductive layer, and ohmic contact is performed between the second metal layer and the p-type conductive layer.
Preferably, the array period of the micro-nano structure array is 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 20-160nm.
Preferably, the resonant cavity is composed of two reflecting mirrors which are arranged correspondingly up and down, wherein the reflectivity of the reflecting mirror which is nearer to the substrate is larger than that of the reflecting mirror which is farther to the substrate.
Preferably, the mirror is one or both of a metal mirror and a distributed Bragg 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 each one of gold, silver, aluminum, copper, platinum, palladium, magnesium or an alloy.
On the other hand, the embodiment of the application also provides a manufacturing method of the RCLED-based sensor, which comprises 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 conductive layer, an active region and a p-type conductive layer in the resonant cavity from bottom to top in sequence;
s103: forming a first metal layer on the substrate or the n-type conductive layer, wherein the first metal layer is conductive with the n-type conductive layer;
s104: forming a second metal layer on the p-type conductive layer, wherein ohmic contact is formed between the second metal layer and the p-type conductive 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 reflecting mirrors which are arranged correspondingly up and down, wherein the reflectivity of the reflecting mirror which is nearer to the substrate is larger than that of the reflecting mirror which is farther to the substrate.
Preferably, the micro-nano structure array in the step S105 is manufactured by adopting 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 the metal hole in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160nm.
From the above technical solutions, the embodiment of the present application has the following advantages:
the embodiment of the application provides a sensor based on an RCLED and a manufacturing method thereof, wherein 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, and meanwhile, the cavity mode with the higher Q value interacts with the micro-nano structure array and can be directly used for detecting the tiny change of refractive index around the metal nano hole array by driving through an external light source, so that the convenient naked eye observation can be realized.
Drawings
FIG. 1 is a flow chart of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
FIG. 2 is a flow chart of a method for manufacturing an RCLED-based sensor according to another embodiment of the present application;
fig. 3 is a cross-sectional view of a sample illustrating step S301 in 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 of an example one of a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 5 is a sample sectional view of step S303 of an example one of a method for manufacturing an RCLED-based sensor according to the embodiment of the present application;
fig. 6 is a cross-sectional view of a sample of step S304, which is an example of a method for manufacturing an RCLED-based sensor according to the embodiment of the present application;
fig. 7 is a cross-sectional view of a sample illustrating step S306 in one example of a method for manufacturing an RCLED-based sensor according to the embodiment of the present application;
fig. 8 is a top view of a sample in 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 an infrared spectrum of a sensor with a resonance wavelength of 650nm in an example one of a method for manufacturing a sensor based on an RCLED according to an embodiment of the present application;
fig. 10 is a cross-sectional view of a sample of example two in a method for manufacturing an RCLED-based sensor according to an embodiment of the present application;
fig. 11 is an infrared spectrum of a sensor with a resonance wavelength of 570nm in an example two in a method for manufacturing a sensor based on an RCLED according to an embodiment of the present application.
Detailed Description
In order to make the present application better understood by those skilled in the art, the following description will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In order to facilitate understanding, the RCLED-based sensor provided by the embodiment 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, and the semiconductor epitaxial layer is arranged in the resonant cavity;
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 may play a supporting role, and a stable metal hole array may 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 surface plasmon resonance coupling effect between holes can be weakened and even the mutual influence can be ignored when the period is too large to cause detuning, and the array period is preferably 300-800nm.
Meanwhile, in a certain range, the smaller the aperture of the metal hole is, the less surface plasmon resonance coupling is generated, and the radius is preferably 60-300nm; the larger the metal thickness in the metal micro-nano structure array, the transmission intensity of the incident light is weakened, and the metal thickness in the metal micro-nano structure array is preferably 20-160nm.
In addition, in this embodiment, the micro-nano structure array of the metal hole array is disposed on the surface of a light emitting diode (RCLED) having a resonant cavity, the light emitting diode emits light to form a cavity mode having a higher Q value through the mode selecting function of the resonant cavity, and meanwhile, the cavity mode having the higher Q value interacts with the micro-nano structure array, and the micro-nano structure array can be directly used for detecting the micro-variation of the refractive index around the metal nano hole array by driving through an external light source, so that convenient naked eye observation can be realized.
The foregoing is one embodiment of an RCLED-based sensor provided by the present application, and the following is another embodiment of an RCLED-based sensor provided by the present application.
The sensor based on the RCLED provided by the embodiment 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, and the semiconductor epitaxial layer is arranged in the resonant cavity;
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 may play a supporting role, and a stable metal hole array may 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.
Further, the RCLED-based sensor further comprises a first metal layer, an n-type conductive layer, an active region and a p-type conductive layer are sequentially arranged on the semiconductor epitaxial layer from bottom to top, ohmic contact is carried out between the first metal layer and the n-type conductive layer, a second metal layer is arranged on the p-type conductive layer, and ohmic contact is carried out between the second metal layer and the p-type conductive layer.
Further, the active region includes a quantum well or a quantum dot.
Further, the array period of the micro-nano structure array is 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 20-160nm.
It should be noted that, the reasonably designed periodic structure can suppress radiation loss, and realize diversity of coupling between metal modes, but the surface plasmon resonance coupling effect between the metal holes will be weakened and even the mutual influence can be ignored when the array period is too large, and preferably, the array period is 300-800nm most suitable.
In addition, in a certain range, the smaller the aperture of the metal hole, the weaker the generated surface plasmon resonance coupling is, and the larger the metal thickness in the metal micro-nano structure array is, the weaker the transmission intensity of incident light is, preferably, the metal thickness in the metal micro-nano structure array is most suitable for 20-160nm.
Further, the resonant cavity is composed of two reflecting mirrors which are arranged up and down correspondingly, wherein the reflectivity of the reflecting mirror which is closer to the substrate is larger than that of the reflecting mirror which is farther from the substrate.
It should be noted that the reflectivity of the mirror may be defined by setting the number of stacked layers of the refractive index material of the mirror, and the mirror may be one or both of a metal mirror and a Distributed Bragg Reflector (DBR), for example, both mirrors may be metal mirrors or distributed bragg reflectors or one may be metal mirrors and the other may be distributed bragg reflectors. Taking a distributed Bragg reflector as an example, the distributed Bragg reflector is a periodic structure formed by alternately arranging two materials with different refractive indexes, namely a material A and a material B, wherein the optical thickness of each layer of material is 1/4 of the central reflection wavelength, and according to lambdaBragg=4nl, lambdaBragg is the central wavelength of a high reflection band of the distributed Bragg reflector, n is the refractive index of the material, and l is the optical thickness of each layer of material, and then a specific central reflection wavelength can be generated by setting the materials with different refractive indexes and the optical thickness of each layer of material.
Further, the dielectric layer is made of silicon nitride, silicon oxide, ITO or other oxide or other nitride dielectric materials.
Further, the first metal layer and the second metal layer are made of one or alloy of gold, silver, aluminum, copper, platinum, palladium and magnesium.
The principle of this embodiment is as follows:
(1) In this embodiment, the use of the RCLED is selected, where the resonant cavity in the RCLED has two functions: firstly, optical feedback capability is provided to form a strong luminescence spectrum, so that the light-emitting efficiency of specific wavelength is improved, and the excitation efficiency of surface plasmons is improved; secondly, a mode selection effect is formed, a high-Q luminous spectrum is obtained, and the light intensity change is larger under the same sensitivity, so that naked eye observation is facilitated; meanwhile, a specific center wavelength is set by utilizing the refractive index and the thickness of the reflecting mirror stacked dielectric layers, the center wavelength can be 300-1200 nm in general, 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 transmitted 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 refractive index around the metal structure affects the change of the resonance wavelength of the surface plasmon, so that the matching degree of the RCLED peak wavelength and the resonance wavelength of the micro-nano array can be adjusted, and the light intensity can be adjusted. Therefore, in this structure, the intensity of light emitted by the RCLED through the micro-nanostructure varies with the refractive index of the surrounding medium. After the corresponding refractive index and the output light intensity are calibrated, the refractive index of the detected object can be obtained through the light intensity change, and the refractive index sensor can be applied to the aspect of the biosensor through a similar principle.
(2) The embodiment is based on a semiconductor resonant cavity light-emitting diode, a strong resonant electric field is generated on the surfaces of a dielectric layer and a metal structure, and an enhanced electric field is generated on the metal surface through energy transportation of nano round holes. By the special design of the resonant cavity mode and the periodic micro-nano structure hole array in the embodiment and the specific limitation of the array period of the periodic micro-nano structure hole array, the radius of the metal holes and the thickness of the metal film, the surface plasma resonance with specific wavelength can be generated on the surface of the micro-nano metal hole array.
(3) Compared with a common LED, the RCLED is adopted, the spectrum of generated light is Gaussian distribution because the spontaneous radiation light of the common LED is not modulated by the resonant cavity, and when the RCLED is used as a sensor, the light interacts with the metal micro-nano array structure, and the RCLED has the effect of moving the peak wavelength, but the light intensity change is much smaller than that of the RCLED under the same sensitivity due to the wide spectrum linewidth, so that the overall effect of naked eye observation is poorer by utilizing the common LED. The existence of the resonant cavity in the RCLED has the function of wavelength selection, and the intensity, the monochromaticity and the polarization characteristic of light corresponding to a 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 specific selected light. In addition, the RCLED has smaller radiation loss at a specific wavelength, higher quality factor and easier and sensitive detection of small changes.
The foregoing is another embodiment of an RCLED-based sensor provided by the present application, and the following is one embodiment of a method for manufacturing an RCLED-based sensor provided by the present application.
For easy understanding, please refer to fig. 1, the method for manufacturing the sensor based on the RCLED according to the present embodiment includes the following steps:
s101: forming a resonant cavity on a substrate;
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, and particularly forming an n-type conductive layer, an active region and a p-type conductive layer in the resonant cavity from bottom to top in sequence;
s103: forming a first metal layer on the substrate or the n-type conductive layer, wherein the first metal layer is conductive with the n-type conductive layer;
it should be noted that, when the substrate forms the first metal layer, ohmic contact is formed between the first metal layer and the substrate, and the substrate may be an n-type conductive layer or conductive with the n-type conductive layer through the substrate; 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 conducted, and an annealing process can be adopted to reduce contact resistance of the first metal layer and the n-type conductive layer.
S104: forming a second metal layer on the p-type conductive layer, wherein ohmic contact is formed between the second metal layer and the p-type conductive layer;
it should be noted that, the ohmic contact between the second metal layer and the p-type conductive layer can reduce the contact resistance of the second metal layer and the p-type conductive layer by adopting an annealing process, and meanwhile, the materials of the first metal layer and the second metal layer can be one of gold, silver, aluminum, copper, platinum, palladium and magnesium or an alloy thereof.
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.
The dielectric layer is made of silicon nitride, silicon oxide, ITO or other oxide or nitride dielectric materials, and plays a role in supporting, 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 between metal modes, but the surface plasmon resonance coupling effect between the metal holes can be weakened and even the mutual influence can be ignored due to the fact that the period is too large, and the array period is preferably 300-800nm.
In a certain range, the smaller the aperture of the metal hole, the weaker the generated surface plasmon resonance coupling, and the larger the thickness of the metal in the metal micro-nano structure array, the weaker the transmission intensity of incident light, preferably, the thickness of the metal in the metal micro-nano structure array is 20-160nm.
The above is one embodiment of a method for manufacturing an RCLED based sensor according to the present application, and the following is another embodiment of a method for manufacturing an RCLED based sensor according to the present application.
Referring to fig. 2, the method for manufacturing the sensor based on the RCLED provided in this embodiment includes the following steps:
s201: forming a resonant cavity on a substrate, wherein the resonant cavity consists of two reflecting mirrors which are arranged up and down correspondingly, and the reflectivity of the reflecting mirror which is nearer to the substrate is larger than that of the reflecting mirror which is farther to the substrate;
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 mirrors may be defined by providing a number of stacked layers of refractive index material of the mirrors, with the mirrors being either one or both of metal mirrors and Distributed Bragg Reflectors (DBRs), e.g., both mirrors being metal mirrors or distributed Bragg reflectors or one being metal mirror and the other being distributed Bragg reflector. Taking a distributed Bragg reflector as an example, the distributed Bragg reflector is a periodic structure formed by alternately arranging two materials with different refractive indexes, namely a material A and a material B, wherein the optical thickness of each layer of material is 1/4 of the central reflection wavelength, and according to lambdaBragg=4nl, lambdaBragg is the central wavelength of a high reflection band of the distributed Bragg reflector, n is the refractive index of the material, and l is the optical thickness of each layer of material, and then a specific central reflection wavelength can be generated by setting the materials with different refractive indexes and the optical thickness of each layer of material.
S202: forming a semiconductor epitaxial layer in the resonant cavity, and particularly forming an n-type conductive layer, an active region and a p-type conductive layer in the resonant cavity from bottom to top in sequence;
s203: forming a first metal layer on the substrate or the n-type conductive layer, wherein the first metal layer is conductive with the n-type conductive layer;
it should be noted that, when the substrate forms the first metal layer, ohmic contact is formed between the first metal layer and the substrate, and the substrate may be an n-type conductive layer or conductive with the n-type conductive layer through substrate conduction; when the first metal layer is formed on the n-type conductive layer, ohmic contact is formed between the first metal layer and the n-type conductive layer, and an annealing process can be adopted to reduce contact resistance of the first metal layer and the n-type conductive layer.
S204: forming a second metal layer on the p-type conductive layer, wherein ohmic contact is formed between the second metal layer and the p-type conductive layer;
it should be noted that, the ohmic contact between the second metal layer and the p-type conductive layer can reduce the contact resistance of the second metal layer and the p-type conductive layer by adopting an annealing process, and meanwhile, the materials of the first metal layer and the second metal layer can be one of gold, silver, aluminum, copper, platinum, palladium and magnesium or an alloy thereof.
S205: the micro-nano structure array is manufactured on the resonant cavity by adopting an electron beam lithography process or a focused ion beam etching process, and comprises a dielectric layer and a metal hole array arranged on the dielectric layer, wherein the array period of the micro-nano structure array is 300-800nm, the radius of a metal hole in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160nm.
The dielectric layer is made of silicon nitride, silicon oxide, ITO or other oxide or nitride dielectric materials, and plays a role in supporting, 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, which comprises the specific steps of exposing the resist of the dielectric layer by utilizing the focused electron beam under the control of a computer according to a preset processing pattern, generating areas with different dissolution performance in the resist, and developing by utilizing selective development according to the dissolution characteristics of the different areas to obtain a required resist pattern; in addition, the micro-nano structure array is manufactured by adopting a focused ion beam etching process, and the metal hole array with the preset structure is obtained by utilizing the focused ion beam etching.
In addition, the reasonably designed periodic structure can inhibit radiation loss, so as to realize the diversity of coupling between metal modes, but the surface plasmon resonance coupling effect between the metal holes can be weakened and even the mutual influence can be ignored when the period is too large, and the array period is preferably 300-800nm.
In addition, the metal hole array is provided with a plurality of metal holes, the smaller the aperture of the metal holes is, the weaker the generated surface plasmon resonance coupling is, and the larger the metal thickness in the metal micro-nano structure array is, the weaker the transmission intensity of incident light is, preferably, the metal thickness in the metal micro-nano structure array is 20-160nm.
The following illustrates some examples of implementations of a method of manufacturing based on an RCLED provided in connection with the present application.
Example one
Taking GaAs-based RCLED with a luminescence center wavelength of 650nm as an example, the present example provides a method for manufacturing a sensor based on an RCLED, comprising the steps of:
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) method 2 High refractive index layer 12 and MgF 2 Low refractive index layer13，TiO 2 High refractive index layer 12 and MgF 2 The low refractive index layer 13 forms a bottom distributed Bragg reflector 14 with 60 layers by setting the material layers, wherein the center reflection wavelength of the bottom distributed Bragg reflector 14 is 650nm, and TiO is set 2 The high refractive index layer 12 has a refractive index n1=2.45, and its physical thickness is 66.3nm; mgF (MgF) 2 The low refractive index layer 13 has a refractive index n2=1.37, and its physical thickness is 118.6nm;
s302: referring to fig. 4, a Ti/Au metal layer 21 is formed on the back surface of the polished or unpolished n-type GaAs substrate 11 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 distributed bragg reflector 14, the GaAs-based semiconductor epitaxial layer is provided with an n-type AlGaAs epitaxial layer 31, a quantum well 32 and a P-type AlGaAs epitaxial layer 33 in this order 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 33 2 High refractive index layer 15 and MgF 2 Low refractive index layer 16, tiO 2 High refractive index layer 15 and MgF 2 The low refractive index layer 16 forms a top distributed Bragg reflector 41 with a sum of layers of 10 layers by setting the number of layers of material;
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 with a thickness of 70nm was evaporated on top of the DBR 41;
s306: referring to fig. 7, an Au layer 51 is evaporated on an oxide ITO layer, and then a photoresist is coated on the Au layer 51, and electron beam exposure and development are performed, to obtain a polymethyl methacrylate (PMMA) square hole array layer 52 uniformly arranged, wherein the array period is 0.6um, and square Kong Bianchang is 0.1um;
s307: and etching a gold film on the polymethyl methacrylate (PMMA) square hole array layer 52 by adopting a reactive ion etching method to form a metal hole array, correspondingly etching an oxide ITO layer, and finally removing PMMA by utilizing an organic solvent to form a micro-nano structure array, wherein reference is made to a top view of a structure in FIG. 8.
Finally, the effect of the RCLED-based sensor formed through the steps S301 to S307 was simulated, wherein 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, the surface of the micro-nano structure array is covered with a dielectric film with a refractive index of n=2.3 of 3nm, which corresponds to adhesion of a layer of biomolecules on the surface. As shown in fig. 9, by comparing the transmission spectrum intensity variations of the uncovered and covered dielectric films, the relative intensity variations ((0.118458-0.02722)/0.118458 = 0.77044) thereof were calculated, whereby it can be judged that the performances of the RCLED-based sensor in the present example were better.
Example two
For easy understanding, please refer to fig. 10, this example takes 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: disposing an AlGaN high refractive index layer 82 and a GaN low refractive index layer 83 on a sapphire substrate 81 by adopting a Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE) method, wherein the AlGaN high refractive index layer 82 and the GaN low refractive index layer 83 form a bottom distributed Bragg reflector 84 with the sum of layers of 40 layers by setting the number of material layers, and the central reflection wavelength of the bottom distributed Bragg reflector 84 is 500nm;
s402: forming a GaN-based semiconductor epitaxial layer on the bottom distributed Bragg reflector 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, and forming an ITO layer on the surface of the P-type GaN epitaxial layer 88, wherein the ITO layer is in ohmic contact with the P-type GaN epitaxial layer 88;
s403: etching the device unit on the semiconductor epitaxial layer and exposing the n-type GaN epitaxial layer 85 at both 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 p-GaN epitaxial layer 88 2 High refractive index layer 89 and SiO 2 Low refractive indexLayer 810, tiO 2 High refractive index layer 89 and SiO 2 The low refractive index layer 810 forms a top distributed Bragg reflector 811 with a sum of layers of 10 layers by setting the number of layers of material;
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 evaporated on the top surface of the top distributed bragg mirror 811, where the thickness is 70nm. And an Au layer 813 is deposited on the surface of the silicon nitride layer 812, and the thickness of the Au layer 813 is 120nm;
s407: spin-coating PMMA on the surface of the Au layer 813, and carrying out electron beam exposure and development to obtain a square hole array pattern PMMA nano hole array, wherein the array period is 0.4um, and the hole radius is 0.1um;
s408: and sequentially etching the silicon nitride layer 812 and the Au layer 813 by adopting a reactive ion etching method, and removing PMMA by utilizing 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, wherein 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, the surface of the Au layer 813 was covered with a 3nm dielectric film having a refractive index of n=2.3, which corresponds to adhesion of a bio-molecular layer on the surface, and the relative intensity change ((0.412684-0.218233)/0.412684 = 0.471186) was calculated by comparing the transmission spectrum intensity changes of the uncovered and covered dielectric films, as shown in fig. 11. The relative intensity change at 650nm resonant wavelength in example one is more pronounced as a result of the relative intensity in example one being 0.77044, which 0.77044 is greater than 0.471186, the higher the sensitivity of the metal nanopore array as it is at longer wavelengths.
In the several embodiments provided by the present application, it should be understood that the disclosed apparatus and method may be implemented in other manners. For example, the apparatus embodiments described above are merely illustrative, e.g., the division of the units is merely a logical function division, and there may be additional divisions when actually implemented, e.g., multiple units or components may be combined or integrated into another system, or some features may be omitted or not performed. Alternatively, the coupling or direct coupling or communication connection shown or discussed with each other may be an indirect coupling or communication connection via some interfaces, devices or units, which may be in electrical, mechanical or other form.
The units described as separate units may or may not be physically separate, and units shown 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 may be selected according to actual needs to achieve the purpose of the solution of this embodiment.
In addition, each functional unit in the embodiments of the present application may be integrated in one processing unit, or each unit may exist alone physically, or two or more units may be integrated in one unit. The integrated units may be implemented in hardware or in software functional units.
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims (6)

1. The sensor based on the 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, and the semiconductor epitaxial layer is arranged in the resonant cavity;
the micro-nano structure array comprises a dielectric layer and a metal hole array arranged on the dielectric layer, wherein the dielectric layer is a patterned dielectric layer, and the shape of the dielectric layer is the same as that of the metal hole array;
the array period of the micro-nano structure array is 300-800nm, the radius of a metal hole in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160 nm;
the resonant cavity consists of two reflecting mirrors which are arranged up and down correspondingly, wherein the reflectivity of the reflecting mirror which is nearer to the substrate is larger than that of the reflecting mirror which is farther to the substrate, and the reflectivity of the reflecting mirror is limited by arranging the stacking layers of refractive index materials of the reflecting mirror.
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, wherein ohmic contact is formed between the first metal layer and the n-type conductive layer, and a second metal layer is arranged on the p-type conductive layer and ohmic contact is formed between the second metal layer and the p-type conductive layer.
3. The RCLED-based sensor of claim 1 wherein the mirror is one or both of a metal mirror and a distributed bragg mirror.
4. The RCLED-based sensor of claim 1, wherein the dielectric layer is silicon nitride, silicon oxide, or ITO.
5. The RCLED-based sensor of claim 2 wherein the first and second metal layers each comprise one of gold, silver, aluminum, copper, platinum, palladium, and magnesium.
6. A method of manufacturing an RCLED-based sensor, comprising the steps of:
s101: forming a resonant cavity on a substrate, wherein the resonant cavity consists of two reflecting mirrors which are arranged up and down correspondingly, the reflectivity of the reflecting mirror which is close to the substrate is larger than that of the reflecting mirror which is far away from the substrate, and the reflectivity of the reflecting mirror is limited by setting the stacking layer number of refractive index materials of the reflecting mirror;
s102: forming a semiconductor epitaxial layer in the resonant cavity, specifically forming an n-type conductive layer, an active region and a p-type conductive layer in the resonant cavity from bottom to top in sequence;
s103: forming a first metal layer on the substrate or the n-type conductive layer, wherein the first metal layer is conductive with the n-type conductive layer;
s104: forming a second metal layer on the p-type conductive layer, wherein ohmic contact is formed between the second metal layer and the p-type conductive layer;
s105: 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, the dielectric layer is a patterned dielectric layer, and the shape of the dielectric layer is the same as that of the metal hole array;
the micro-nano structure array in the step S105 is manufactured by adopting 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 a metal hole in the metal hole array is 60-300nm, and the metal thickness of the micro-nano structure array is 20-160nm.
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