CN113809192B - Trapezoidal gallium nitride micrometer line array photoelectric detector and preparation method thereof - Google Patents

Trapezoidal gallium nitride micrometer line array photoelectric detector and preparation method thereof Download PDF

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CN113809192B
CN113809192B CN202110920163.1A CN202110920163A CN113809192B CN 113809192 B CN113809192 B CN 113809192B CN 202110920163 A CN202110920163 A CN 202110920163A CN 113809192 B CN113809192 B CN 113809192B
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gallium nitride
silicon dioxide
micro
dioxide insulating
groove structure
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CN113809192A (en
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李京波
孙一鸣
王小周
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Zhejiang Xinke Semiconductor Co Ltd
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Abstract

The invention discloses a trapezoid gallium nitride micrometer line array photoelectric detector and a preparation method thereof, wherein the detector comprises the following components: a silicon substrate; silicon dioxide insulating layers are formed on the silicon substrate at intervals, so that a plurality of groove structures are formed on the substrate which is not covered by the silicon dioxide insulating layers; a gallium nitride nanowire formed in the groove structure, wherein the extending direction of the nanowire is consistent with that of the groove structure, and the gallium nitride nanowire is higher than the silicon dioxide insulating layer; the aluminum nitride buffer layer is formed inside the gallium nitride micron line of the groove structure; and the metal electrodes are arranged above the gallium nitride micro-wires and the silicon dioxide insulating layer and are perpendicular to the direction of the groove structure. The photoelectric detector has the advantages of high light/dark current, rapid response, high on/off current ratio, wide detection range and the like, and the device structure is easy to grow and manufacture.

Description

Trapezoidal gallium nitride micrometer line array photoelectric detector and preparation method thereof
Technical Field
The invention belongs to the field of semiconductors, and particularly relates to a trapezoidal gallium nitride micrometer line array photoelectric detector and a preparation method thereof.
Background
A photodetector is a semiconductor device based on the photoelectric effect, which can absorb a certain amount of energy under the light radiation to complete the conversion from an optical signal to an electrical signal. Photodetectors are widely used, involving a number of fields of military, communication, medical, etc., such as: night vision device, missile guidance, fire detection, etc.
Gallium nitride (GaN) is used as a model of a third-generation semiconductor, and is a group iii nitride, insoluble in water at room temperature, resistant to strong acids and strong bases, and soluble in alkaline solutions at high temperatures only at a slow rate, so that the stable physicochemical properties of the gallium nitride material enable devices made of the gallium nitride material to operate normally in certain hostile environments. There have been many studies on GaN-based detectors of different structures, which are classified into a photovoltaic type detector and a photoconductive type detector according to the operation mode, wherein the photovoltaic type detector is a junction type device and the photoconductive type detector is a junction-free type device. The photoconductive detector mainly works by utilizing the photoconductive effect of semiconductor materials, and the basic principle is that when the energy generated by illumination is larger than the forbidden band width of the semiconductor, unbalanced photon-generated carriers are generated due to intrinsic absorption and impurity absorption, so that the resistivity of the semiconductor materials is changed, and the photoconductive detector is similar to a photoresistor in practice. The photoconductive detector has advantages of simple structure, easy manufacture, fast response speed, etc., but has disadvantages of large dark current.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a trapezoidal gallium nitride micrometer line array photoelectric detector and a preparation method thereof. The technical problems to be solved by the invention are realized by the following technical scheme:
A preparation method of a trapezoid gallium nitride micrometer line array photoelectric detector comprises the following steps:
S1, providing a silicon substrate;
s2, depositing a silicon dioxide insulating layer on the silicon substrate;
S3, etching the silicon dioxide insulating layer to form a plurality of groove structures for growing the micro-wires;
s4, epitaxially growing a gallium nitride micron line in the groove structure and enabling the gallium nitride micron line to be higher than the silicon dioxide insulating layer, wherein the extending direction of the micron line is consistent with that of the groove structure;
S5, evaporating a plurality of metal electrodes on the surface of the micrometer wire.
In a specific embodiment, the step S4 further includes:
And epitaxially growing an aluminum nitride buffer layer in the groove structure by a metal organic chemical vapor deposition method so as to epitaxially grow gallium nitride micro-wires on the aluminum nitride buffer layer.
In a specific embodiment, the step S3 includes:
S31, spin-coating a layer of photoresist on the surface of the silicon dioxide insulating layer, and forming a periodically arranged strip-shaped epitaxial pattern on the surface of the silicon dioxide insulating layer after pre-baking, exposure, post-baking and development;
S32, selectively etching the silicon dioxide insulating layer according to the strip-shaped epitaxial pattern, and then removing photoresist from the silicon dioxide insulating layer to obtain a plurality of groove structures for growing the micro-wires.
In one specific embodiment, the step S5 includes:
The Ti/Al/Ti/Au metal is evaporated or sputtered by magnetron sputtering on the surface of the silicon substrate provided with the gallium nitride micro-wire by a thermal evaporation or magnetron sputtering process to form a plurality of metal electrodes, and the interval between two adjacent metal electrodes is 5-20 mu m.
The invention also provides a trapezoid gallium nitride micrometer line array photoelectric detector, which comprises:
A silicon substrate;
A silicon dioxide insulating layer formed on the silicon substrate, wherein the silicon dioxide insulating layer is provided with a plurality of groove structures;
A gallium nitride nanowire formed in the groove structure, wherein the extending direction of the nanowire is consistent with that of the groove structure, and the gallium nitride nanowire is higher than the silicon dioxide insulating layer;
The aluminum nitride buffer layer is formed inside the gallium nitride micron line of the groove structure;
the metal electrodes are arranged above the gallium nitride micro-wire and the silicon dioxide insulating layer and are perpendicular to the direction of the groove structure, wherein the cross section of the groove structure is rectangular, the cross section of the gallium nitride micro-wire is trapezoid, and the distance between two adjacent metal electrodes is 5-20 mu m.
In a specific embodiment, the width of the groove structures is 5-10 μm, the depth of the groove structures is 3.5-5 μm, and the distance between every two groove structures is 8-10 μm.
In a specific embodiment, the gallium nitride nanowires have a height of 4-6 μm.
In one embodiment, the thickness of the aluminum nitride buffer layer is 20-200nm.
In one embodiment, the thickness of the silicon dioxide insulating layer is 200-400nm.
The invention has the beneficial effects that:
The trapezoidal gallium nitride micro-wire array photoelectric detector adopts a mode of growing trapezoidal gallium nitride micro-wires between grooves formed by the insulating layers, and the trapezoidal gallium nitride micro-wires grown in the grooves can fully utilize the limited silicon substrate area, so that higher crystal quality is obtained, the body surface area ratio is increased, and meanwhile, defects caused by lattice mismatch and thermal mismatch are greatly reduced. The structure increases the light receiving area of the detector, so that the detector can fully absorb energy and generate more unbalanced photo-generated carriers, thereby increasing the response speed of the detector and improving the light/dark current ratio. The photoelectric detector has the advantages of high light/dark current ratio, rapid response, high on/off current ratio and wide detection range, and the device structure is easy to grow and manufacture.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic flow chart of a method for manufacturing a trapezoidal gallium nitride micro-line array photoelectric detector according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a trapezoidal gallium nitride micro-line array photodetector according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a substrate structure of a trapezoidal gallium nitride micro-wire array photodetector provided by the invention, wherein the substrate structure is etched when trapezoidal gallium nitride micro-wires are not grown;
Fig. 4 is a schematic diagram of a substrate structure of a trapezoidal gallium nitride micro-wire array photodetector with a trapezoidal gallium nitride micro-wire epitaxially grown thereon;
Fig. 5 is a schematic cross-sectional view of the substrate of fig. 3 without trapezoidal gallium nitride nanowires grown;
FIG. 6 is a schematic cross-sectional view of the trapezoidal gallium nitride nanowire of FIG. 3 grown;
FIG. 7 is a cross-sectional view of the photodetector of FIG. 2;
FIG. 8 is a graph showing the I-T (portion) of a GaN microwire array photodetector of the present invention under 5V applied voltage, 325nm,1mw/cm2 light irradiation;
FIG. 9 is an I-V diagram of a GaN micro-line array photodetector according to the present invention under different light power of 325 nm.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Example 1
Referring to fig. 1, fig. 1 is a schematic flow chart of a preparation method of a trapezoidal gallium nitride micro-line array photoelectric detector according to an embodiment of the invention, including:
s1, providing a silicon substrate, specifically, adopting a 2-inch intrinsic silicon wafer as a substrate, wherein the silicon substrate is a high-resistance silicon wafer (the resistivity is more than 10 5 ohm cm), and the crystal orientation of the silicon wafer is <100>.
S2, depositing a silicon dioxide insulating layer on the silicon carbide substrate; in this example, a 200nm insulating layer of silicon dioxide may be formed on a 2 inch wafer surface by thermal reduction.
S3, etching the silicon dioxide insulating layer to form a plurality of groove structures for growing the micro-wires, wherein the width of each groove structure is 5-10 mu m, the depth of each groove structure is 3.5-5 mu m, and the interval between every two groove structures is 10 mu m;
The specific step S3 is as follows:
s31, spin-coating a layer of photoresist on the surface of the silicon dioxide insulating layer, and forming a periodically arranged strip-shaped epitaxial pattern on the surface of the silicon dioxide insulating layer after pre-baking, exposure, post-baking and development; wherein the photoresist thickness is 2 μm; the stripe interval width of the stripe-shaped epitaxial pattern is 10 mu m;
S32, selectively etching the silicon dioxide insulating layer according to the strip-shaped epitaxial pattern, and then removing photoresist from the insulating layer to obtain a plurality of groove structures for growing the micro-wires.
The specific treatment process comprises the steps of selectively etching the upper surface of the silicon carbide substrate according to the periodically arranged strip-shaped epitaxial patterns, and then performing photoresist stripping treatment on the silicon carbide substrate; during selective etching, the silicon dioxide insulating layer without photoresist protection is etched by using a buffer etching solution (BOE solution) to form a 10-mu m silicon carbide substrate and a 10-mu m photoresist-protected silicon dioxide layer which alternately appear, then acetone and isopropanol are used for photoresist removal, deionized water is used for cleaning, and a nitrogen gun is used for drying the surface of the substrate to finally form a plurality of groove structures.
And S4, epitaxially growing a gallium nitride micron line in the groove structure and enabling the gallium nitride micron line to be higher than the silicon dioxide insulating layer, wherein the extending direction of the micron line is consistent with the extending direction of the groove structure. Particularly, the cross section of the gallium nitride micro-wire is trapezoid; one side of the trapezoid is contacted with the bottom of the groove; the growth height of the gallium nitride micro-wires is preferably 4-6 mu m, so that the grown gallium nitride micro-wires are higher than the insulating layer, thereby avoiding the situation that the metal fully covers the gallium nitride micro-wires after electrode plating.
Preferably, the gallium nitride micro-wire is epitaxially grown in the groove structure by a metal organic chemical vapor deposition method, an aluminum nitride buffer layer with the thickness of 20-200nm is epitaxially grown in the groove structure, and then the gallium nitride micro-wire is epitaxially grown on the aluminum nitride buffer layer. The aluminum nitride buffer layer has the effect that the quality of the grown gallium nitride is better; the aluminum nitride buffer layer can prevent current from flowing out of the silicon substrate, thereby playing an insulating role. The thickness of the aluminum nitride buffer layer is set to 20-200nm, and if the thickness of the aluminum nitride buffer layer is less than 20nm, it cannot play an insulating role, and if it is more than 200nm, a piece of aluminum nitride is formed on the groove and the insulating layer 20, resulting in an increase in dark current.
The grooves of the embodiment are rectangular in structure, and the micrometer wires are arranged in the grooves, so that the process is simpler when the subsequent electrode grows. In addition, the embodiment does not need to etch the silicon substrate, so that the process flow is further simplified, and the cost is greatly reduced.
S5, evaporating a plurality of metal electrodes on the surface of the micrometer wire;
The step can be implemented by evaporating or sputtering Ti/Al/Ti/Au metal on the surface of the silicon substrate provided with the gallium nitride micro-wire through a thermal evaporation or magnetron sputtering process to form a plurality of metal electrodes, and the distance between two adjacent metal electrodes is 10 mu m.
In addition, the existing preparation needs to introduce multiple etching (such as a groove gate structure) or secondary epitaxy (such as a growth cap layer), and the preparation processes such as etching can cause mechanical damage, so that the gate leakage current is increased; impurities can be introduced into the second epitaxy, so that interface defects are caused, a large number of dislocation and the like are generated; the damage to the device caused by the processes is large, so that defects are increased, the performance of the device is affected, the mass production of the device is not facilitated, and the cost is high. The method has the advantages of simple growth process, no introduction of etching, low cost, high process repeatability and consistency and the like.
Example two
Referring to fig. 2-7, a trapezoidal gallium nitride micro line array photodetector according to the present embodiment can be manufactured by the method of embodiment one, and the device includes:
A silicon substrate 10;
a silicon dioxide insulating layer 20 formed on the silicon substrate 10 at intervals so that a plurality of groove structures 201 are formed on the substrate not covered with the silicon dioxide insulating layer 20;
A plurality of gallium nitride micro wires 30 formed in the groove structure 201, wherein the extending direction of the gallium nitride micro wires 30 is consistent with the extending direction of the groove structure 201, and the gallium nitride micro wires 30 are higher than the silicon dioxide insulating layer 20, and the gallium nitride micro wires 30 are in an array shape;
An aluminum nitride buffer layer 50 formed inside the gallium nitride micron line 30 of the groove structure 201; the aluminum nitride buffer layer 50 can enable the grown gallium nitride to obtain better crystal quality; the aluminum nitride buffer layer 50 serves as an insulator because it can prevent current from flowing out of the silicon substrate.
The metal electrodes 40 are disposed above the gan microwire 30 and the silicon dioxide insulating layer 20 and perpendicular to the direction of the groove structure 201, and are in an array shape, wherein the cross section of the groove structure 201 is rectangular, the cross section of the gan microwire 30 is trapezoid, and the distance between two adjacent metal electrodes 40 is 5-20 μm. The groove structure 201 has the function of limiting the growth area and shape of the micro-wire, and the rectangular groove enables the micro-wire to grow into the micro-wire with the trapezoid cross section better, and can avoid a large number of defects and improve the crystal quality.
The manner of growing the gallium nitride micro-wire in the groove structure 201 can fully utilize the effective area of the silicon substrate, so that the volume surface area ratio is increased, and the gallium nitride micro-wire grows in a limited area in the groove structure 201, so that defects caused by unnecessary lattice mismatch and thermal mismatch can be reduced, and higher crystal quality is obtained. The structure increases the light receiving area of the detector, so that the detector can fully absorb energy and generate more unbalanced photo-generated carriers, thereby increasing the response speed of the detector and improving the light/dark current ratio. The photoelectric detector has the advantages of high light/dark current ratio, rapid response, high on/off current ratio and wide detection range, and the device structure is easy to grow and manufacture.
The working process of the photoelectric detector is as follows: absorbing optical radiation through the gallium nitride micron lines 30 to produce unbalanced photogenerated carriers; the additional electrons generated are collected at the metal electrode 40, causing a change in the resistivity of the gan microwires.
In particular, the gallium nitride micron line 30 has a trapezoidal cross section; one side of the trapezoid contacts with the bottom of the groove structure 201; the growth height of the gan microwire 30 is preferably 4-6 μm, so that the grown gan microwire is slightly higher than the silicon dioxide insulating layer, thereby avoiding the occurrence of metal-fully covered gan microwires after electrode plating.
As a preferred embodiment, the bottom of the gan microwire 30 and the groove structure 201 is provided with an aluminum nitride buffer layer 50, and the thickness of the aluminum nitride buffer layer 50 is 20-200nm. The aluminum nitride buffer layer 50 acts to make the quality of the grown gallium nitride better; the aluminum nitride buffer layer 50 prevents current from flowing from the silicon substrate, thereby functioning as an insulator. The thickness of the aluminum nitride buffer layer 50 is set to 20-200nm, and if the thickness of the aluminum nitride buffer layer 50 is less than 20nm, it cannot perform an insulation function, and if it is more than 200nm, a piece of aluminum nitride is formed on the groove and the insulation layer 20, resulting in an increase in dark current.
As a preferred embodiment, the groove structures 201 are preferably rectangular grooves, i.e. the cross section is rectangular, the width of the groove structures 201 is 5-10 μm, the depth of the groove structures 201 is 3.5-5 μm, and the distance between every two groove structures 201 is 10 μm. The groove structure 201 has the function of limiting the growth area and shape of the micro-wires, the rectangular groove enables the micro-wires to grow into micro-wires with trapezoid cross sections, the problem that a large number of defects occur due to overlapping of films of the thin film structure and large-area lattice mismatch is avoided, and the crystal quality is improved.
In order to better illustrate the effect of the present embodiment, please refer to fig. 8-9, the photo detector provided in the present embodiment is irradiated with light of 5v,325nm,1mw/cm 2 applied voltage, and the photo current drop time is 17ms when the light source is removed; after the light source is re-supplied, the rising time of the photocurrent is 18ms; under an applied voltage of 5V, the current under no illumination (dark current) was 10 -11 A, and the current under light irradiation of 325nm (photocurrent). The current was increased by a factor of 200 under irradiation with light of 325nm,1mw/cm 2. (note: rise time means time required for dark current to rise to 90% of steady current when illumination is given, fall time means time required for current to fall to 10% of original steady when illumination is removed. MW/cm 2 means optical power density means intensity of illumination radiation received per square centimeter, and the larger the optical power density means that illumination is stronger).
Because the film material has lattice mismatch, thermal mismatch and other problems in the growth process, a large number of defects and dislocation are generated in the epitaxial film, and the device performance is reduced; the microwire prepared by the embodiment overcomes the problems of the thin film material, can obtain a microwire array with high crystal quality, and improves the performance of devices.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
Although the application is described herein in connection with various embodiments, other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed application, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the "a" or "an" does not exclude a plurality. A single processor or other unit may fulfill the functions of several items recited in the claims. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.

Claims (8)

1. The preparation method of the trapezoid gallium nitride micro-line array photoelectric detector is characterized by comprising the following steps of:
S1, providing a silicon substrate;
s2, depositing a silicon dioxide insulating layer on the silicon substrate;
S3, etching the silicon dioxide insulating layer to form a plurality of groove structures for growing the micro-wires;
S4, epitaxially growing a gallium nitride micro-wire in the groove structure and enabling the gallium nitride micro-wire to be higher than the silicon dioxide insulating layer, wherein the extending direction of the gallium nitride micro-wire is consistent with that of the groove structure, the cross section of the gallium nitride micro-wire is trapezoid, the height of the trapezoid is perpendicular to the plane where the silicon substrate is located, and the lower bottom of the trapezoid is in contact with the bottom of the groove;
s5, evaporating a plurality of metal electrodes on the surface of the micrometer wire, wherein the extending direction of the metal electrodes is perpendicular to the extending direction of the groove structure;
the step S3 comprises the following steps:
S31, spin-coating a layer of photoresist on the surface of the silicon dioxide insulating layer, and forming a periodically arranged strip-shaped epitaxial pattern on the surface of the silicon dioxide insulating layer after pre-baking, exposure, post-baking and development;
S32, selectively etching the silicon dioxide insulating layer according to the strip-shaped epitaxial pattern, and then removing photoresist from the silicon dioxide insulating layer to obtain a plurality of groove structures for growing the micro-wires.
2. The method for manufacturing a trapezoidal gallium nitride micro-line array photoelectric detector according to claim 1, wherein the step S4 is preceded by the following steps:
And epitaxially growing an aluminum nitride buffer layer in the groove structure by a metal organic chemical vapor deposition method so as to epitaxially grow gallium nitride micro-wires on the aluminum nitride buffer layer.
3. The method for manufacturing a trapezoidal gallium nitride micro-line array photoelectric detector according to claim 1, wherein the step S5 includes:
The Ti/Al/Ti/Au metal is evaporated or sputtered by magnetron sputtering on the surface of the silicon substrate provided with the gallium nitride micro-wire by a thermal evaporation or magnetron sputtering process to form a plurality of metal electrodes, and the interval between two adjacent metal electrodes is 5-20 mu m.
4. A trapezoidal gallium nitride micro-line array photodetector, comprising:
A silicon substrate;
Silicon dioxide insulating layers are formed on the silicon substrate at intervals, so that a plurality of groove structures are formed on the substrate which is not covered by the silicon dioxide insulating layers;
A gallium nitride nanowire formed in the groove structure, wherein the extending direction of the nanowire is consistent with that of the groove structure, and the gallium nitride nanowire is higher than the silicon dioxide insulating layer;
The aluminum nitride buffer layer is formed inside the gallium nitride micron line of the groove structure;
The metal electrodes are arranged above the gallium nitride micro-wire and the silicon dioxide insulating layer and are perpendicular to the direction of the groove structure, the cross section of the groove structure is rectangular, the cross section of the gallium nitride micro-wire is trapezoid, the height of the trapezoid is perpendicular to the plane where the silicon substrate is located, the lower bottom is in contact with the bottom of the groove, and the distance between two adjacent metal electrodes is 5-20 mu m.
5. The trapezoidal gallium nitride micro line array photodetector according to claim 4, wherein the width of the groove structure is 5-10 μm, the depth of the groove structure is 3.5-5 μm, and the distance between every two groove structures is 8-10 μm.
6. The trapezoidal gallium nitride micro wire array photodetector of claim 4, wherein the height of the gallium nitride micro wire is 4-6 μm.
7. The trapezoidal gallium nitride micro line array photodetector of claim 4, wherein said aluminum nitride buffer layer has a thickness of 20-200nm.
8. The trapezoidal gallium nitride micro line array photodetector of claim 4, wherein said silicon dioxide insulating layer has a thickness of 200-400nm.
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