CN104634767B - Manufacturing method of gallium nitride (GaN) based resonant cavity gas sensor - Google Patents

Manufacturing method of gallium nitride (GaN) based resonant cavity gas sensor Download PDF

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CN104634767B
CN104634767B CN201510094227.1A CN201510094227A CN104634767B CN 104634767 B CN104634767 B CN 104634767B CN 201510094227 A CN201510094227 A CN 201510094227A CN 104634767 B CN104634767 B CN 104634767B
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gas sensor
resonant cavity
gallium nitride
containing layer
preparation
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CN104634767A (en
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张保平
翁国恩
梅洋
张江勇
应磊莹
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Xiamen University
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Xiamen University
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Abstract

The invention relates to a gas sensor and particularly relates to a manufacturing method of a gallium nitride (GaN) based resonant cavity gas sensor. The manufacturing method comprises the following steps: manufacturing a first graphical distributed Bragg reflector on a GaN based epitaxial wafer with sapphire which serves as a substrate, and forming a first metal containing layer on the surface of the graphical distributed Bragg reflector in an evaporating or sputtering way; forming a second first metal containing layer on the surface of the substrate by adopting an evaporating or sputtering method; bonding the first metal containing layer with the second first metal containing layer in vacuum or the atmosphere of nitrogen, and removing the substrate by adopting a laser stripping technology; separating the GaN based epitaxial wafer from which the substrate is removed to form a two-dimensional array structure, then manufacturing a metal electrode and a second distributed Bragg reflector by adopting an evaporating or sputtering method, and finally depositing a polymer coating to obtain the GaN based resonant cavity gas sensor. The gas sensor can be manufactured into a two-dimensional array structure, can achieve the purpose of detecting various gases simultaneously and is low in cost and high in detection sensitivity and efficiency. In the GaN based resonant cavity structure, the gas sensor can be used for determining the content of the detected gas according to the shift of resonant light wavelength. The gas sensor is simple in principle and high in detection sensitivity and is easy to manufacture.

Description

A kind of preparation method of gallium nitride based resonant cavity gas sensor
Technical field
The present invention relates to gas sensor, especially relate to a kind of preparation side of gallium nitride based resonant cavity gas sensor Method.
Background technology
Gallium nitride-based material belongs to direct band-gap semicondictor material and has continuously adjustable band gap, emission wavelength under room temperature Cover near-infrared, visible ray and deep ultraviolet band, be third generation semi-conducting material.Due to its stable mechanically and chemically property Can, based on gallium nitride-based material make photoelectric device illumination, total colouring, optical storage, signal detection, laser printing with And communication etc. field be with a wide range of applications.
Gas sensor is study hotspot in recent years, and one of its purposes is for detecting that in environment, noxious volatile is organic Thing gas (such as formaldehyde and acetone etc.) content, this is very important to the health of the people working in specific environment.At present The signal transduction mechanism for detecting these volatile organic matter gas contents of report mainly includes polymer coating cantilever (polymer coated cantilevers), film resistor (thin-film resistors) and optical fiber (optical (H.Jensenius, J.Thaysen, et al., the A microcantilever-based alcohol vapor such as fibers) sensor-application and response model,Appl.Phys.Lett.,76:2615(2000);J.Li, Y.Lu,et al.,Carbon nanotube sensors for gas and organic vapor detection,Nano Lett.,3:929(2003);D.K.C.Wu,B.T.Kuhlmey,et al.,Ultrasensitive photonic crystalrefractive index sensor,Opt.Lett.,34:322 (2009)), these detection methods all have very high Response sensitivity.The method of wherein deposited polymer has the advantage of uniqueness, it is advantageous that polymer and volatile organic matter There is one-to-one relation in the response between gas, can realize detection simultaneously many by depositing different polymer coatings Plant the purpose of organic gas content, improve detection efficiency and reduce cost.
Content of the invention
It is an object of the invention to provide a kind of preparation method of gallium nitride based resonant cavity gas sensor.
The present invention comprises the following steps:
1) make graphical distribution Bragg reflector on Sapphire Substrate GaN base epitaxial wafer, then in surface evaporation Or sputtering the first metal-containing layer;
2) in substrate surface evaporation or sputtering the second metal-containing layer;
3) the first metal-containing layer and the second metal-containing layer are fitted, be bonded under vacuum or nitrogen atmosphere, then pass through laser Lift-off technology removes Sapphire Substrate;
4) device isolation is carried out to the GaN base epitaxial wafer removing after Sapphire Substrate, form two-dimensional array structure, then steam Send out or splash-proofing sputtering metal electrode, distribution Bragg reflector, last deposited polymeric coatings, complete element manufacturing.
In step 1) in, the graphical distribution Bragg reflector of described making can be using photoetching, stripping, corrosion or etching etc. Method;Described distribution Bragg reflector is formed by the staggered superposition of deielectric-coating of two kinds of different refractivities, the thickness of every layer dielectric Degree can be 1/4 centre wavelength, and deielectric-coating combination can adopt TiO2/SiO2Or Ta2O5/SiO2Deng;
The composition of described first metal-containing layer can at least one in the conventional bond wire such as Au, In, Sn, Cu, Pb or At least two alloy.
In step 2) in, described substrate can adopt silicon chip etc.;The composition of described second metal-containing layer can for Au, In, Sn, At least one in the conventional bond wire such as Cu, Pb or at least two alloy.
In step 4) in, described device isolation can be using corrosion or sense coupling method;Described metal Electrode can adopt Ni/Au, Cr/Au or Ti/Au etc.;Described metal electrode, distribution Bragg reflector, polymer coating can adopt The methods such as photoetching, stripping, corrosion or etching;The selection of described polymer coating depends on detected gas, this polymer coating Allow for causing the change of thickness and refractive index after absorbing detected gas, such as detect acetone and can select polystyrene Deng.
The present invention provides a kind of preparation scheme of new gallium nitride based resonant cavity gas sensor, is had using Polymer absorption The reflectivity to change resonator upper reflector for the change of thickness and refractive index after machine thing gas, thus cause resonant radiation wavelength Movement, the knots modification according to emission wavelength is determining the content of detected gas.It is an advantage of the current invention that gallium nitride base material Material there is stable mechanically and chemically property, can in various adverse circumstances normal work.This sensor detects spirit simultaneously Sensitivity height, it is easy to be fabricated to two-dimensional array structure, reaches the purpose simultaneously detecting multiple gases, reduces cost, improves efficiency.
The present invention is based on gallium nitride based resonant cavity structure, and the movement using device resonant radiation wavelength determines detected gas Body burden, principle is simple, makes easily and detectivity is high, be a kind of new gas sensor having a extensive future.
The present invention can easily realize the two-dimensional array arrangement of sensor, realize detecting multiple volatile organic matter gas simultaneously Body.Cleaning Principle is simply expressed as follows:After polymer coating absorbs specific organic gas, its thickness and refractive index can be sent out Raw change.Because these polymer are deposited directly on the upper reflector of resonator, the two can regard the whole of a unification as Body, polymer thickness is changed the change of the reflectivity causing resonator upper reflector with refractive index, thus leading to resonator Resonant radiation wavelength be moved.Refraction index changing is bigger, and wavelength movement is more obvious.According to this principle, find out resonance and send out Quantitative relationship between optical wavelength knots modification and the concentration of organic gas of absorption is it is possible to pass through the resonant radiation ripple of sensor Long knots modification Δ λ is determining the concentration of certain organic gas in environment.
Brief description
Fig. 1 is the gallium nitride-based epitaxial chip architecture schematic diagram being used;
Fig. 2 is to make graphical distribution Bragg reflector schematic diagram on p-type gallium nitride;
Fig. 3 is metal bonding schematic diagram;
Fig. 4 removes the schematic diagram after Sapphire Substrate and sense coupling discrete device for laser lift-off;
Fig. 5 is gallium nitride based resonant cavity light emitting devices two-dimensional array schematic diagram;
Fig. 6 is gas sensor two-dimensional array schematic diagram after deposited polymeric coatings.
Specific embodiment
Describe the technological process of the present invention below in conjunction with accompanying drawing in detail.
1) as shown in figure 1, MOCVD method is adopted on Sapphire Substrate 11, grow GaN low temperature buffer layer successively (30nm), unadulterated GaN layer (2.5 μm), the n-type GaN layer (2.5 μm) mixing Si, InGaN/GaN multiple quantum well active layer (2nm/5nm × 5), mix the AlGaN layer (200nm) of Mg and mix the GaN base epitaxial layers 12 such as the p-type GaN layer (800nm) of Mg, and Carry out high annealing, to improve hole concentration after the completion of epitaxial wafer growth.
2) as Fig. 2, photoetching is carried out to described epitaxial wafer, then adopt electron beam evaporation or magnetically controlled sputter method growth distribution Bragg mirror, recycles the method peeled off to obtain patterned distribution Bragg reflector 21;Distribution Bragg reflector By 25 layers of Ta2O5/SiO2Stacking forms, and every layer dielectric thickness is 1/4 centre wavelength, and reflectivity is more than 99%.
3) evaporate 4 μm of the first metal-containing layer (Au) 31 in distribution Bragg reflector side, on clean silicon chip 33 Evaporate the second metal-containing layer (Au) 32;Vacuum environment, 350 DEG C, under 4MPa pressure, first, second is bonded in one containing layer gold Rise, as shown in Figure 3.
4) using laser lift-off technique, Sapphire Substrate is removed, gallium nitride-based epitaxial structure is transferred to silicon chip substrate On, and with sense coupling method, gallium nitride-based epitaxial structure is separated, as shown in Figure 4.
5) using and step 2) in identical method make N-shaped metal electrode 51 and graphical distribution Bragg reflector 52, form complete cavity resonator structure, as shown in Figure 5.Here the reflectivity of distribution Bragg reflector 52 is slightly below distributed cloth The reflectivity of glug speculum 21.
6) the last upper reflector surface deposited polymeric coatings 61 in resonator, complete the preparation of gas sensor, such as Shown in Fig. 6.
On gallium nitride based resonant cavity upper reflector, the polymer coating of deposition can be same polymer or several Plant different polymer arrays.
GaN base epitaxial wafer can using molecular beam epitaxy, metal-organic chemical vapor extension, hydride gas-phase epitaxy or Prepared by the methods such as person's magnetron sputtering.
The present invention passes through to deposit one layer of special polymer on the upper reflector surface of gallium nitride based resonant cavity light emitting devices Coating is realizing.This gas sensor mainly for detection of the concentration of harmful volatile organic matter in environment, such as formaldehyde and Acetone etc..Because gallium nitride-based material has stable mechanically and chemically performance, therefore this sensor can adapt to various evils Bad environment.During this sensor energising work, there is the resonant radiation wavelength X of a fixation when not absorbing detected gas, when After polymer coating absorbs detected organic gas, the thickness of polymeric layer and refractive index can change, so that sensor Resonant radiation wavelength be changed into λ '.Knots modification Δ λ=λ '-λ according to resonance wavelength before and after absorption gas is it is possible to determine environment In detected organic gas concentration.The advantage of this gas sensor also resides in and is easily achieved two-dimensional array structure, that is, pass through Deposit different polymer coatings to realize detecting multiple gases simultaneously, drastically increase detection efficiency reducing and be fabricated to This.

Claims (12)

1. a kind of preparation method of gallium nitride based resonant cavity gas sensor is it is characterised in that comprise the following steps:
1) make graphical distribution Bragg reflector on Sapphire Substrate GaN base epitaxial wafer, then in surface evaporation or splash Penetrate the first metal-containing layer;
2) in sapphire substrate surface evaporation or sputtering the second metal-containing layer;
3) the first metal-containing layer and the second metal-containing layer are fitted, be bonded under vacuum or nitrogen atmosphere, then pass through laser lift-off Technology removes Sapphire Substrate;
4) device isolation carried out to the GaN base epitaxial wafer removing after Sapphire Substrate, forms two-dimensional array structure, then evaporation or Splash-proofing sputtering metal electrode, distribution Bragg reflector, last deposited polymeric coatings, complete element manufacturing.
2. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 1), in, the graphical distribution Bragg reflector of described making adopts photoetching, stripping, corrosion or lithographic method.
3. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 1), in, described distribution Bragg reflector is formed by the staggered superposition of deielectric-coating of two kinds of different refractivities, the thickness of every layer dielectric Spend for 1/4 centre wavelength, deielectric-coating combination adopts TiO2/SiO2Or Ta2O5/SiO2.
4. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 1) in, at least one consisting of in Au, In, Sn, Cu, Pb bond wire of described first metal-containing layer.
5. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 1) in, described first metal-containing layer consist of in Au, In, Sn, Cu, Pb bond wire at least two alloy.
6. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 2) in, at least one consisting of in Au, In, Sn, Cu, Pb bond wire of described second metal-containing layer.
7. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 2) in, described second metal-containing layer consist of in Au, In, Sn, Cu, Pb bond wire at least two alloy.
8. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 4), in, described device isolation is using corrosion or sense coupling method.
9. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 4), in, described metal electrode adopts Ni/Au, Cr/Au or Ti/Au.
10. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 4), in, described metal electrode, distribution Bragg reflector, polymer coating adopt photoetching, stripping, corrosion or lithographic method.
11. as claimed in claim 1 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that in step 4), in, the selection of described polymer coating depends on detected gas, and this polymer coating is necessary after absorbing detected gas The change of thickness and refractive index can be caused.
12. as claimed in claim 11 a kind of preparation method of gallium nitride based resonant cavity gas sensor it is characterised in that described Detected gas is acetone, and polymer coating selects polystyrene.
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CN107887790A (en) * 2017-09-27 2018-04-06 华东师范大学 A kind of multi-wavelength GaN base asymmetric quantum well surface-emitting laser and preparation method thereof
CN111063725B (en) * 2019-12-19 2021-01-19 太原理工大学 Three-dimensional gallium nitride-based exhalation type gas sensor and preparation method thereof
CN114076739B (en) * 2020-08-21 2023-09-12 广东工业大学 RCLED-based sensor and manufacturing method thereof

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