CN115000244B - Manufacturing method of high-performance self-driven GaN nanowire ultraviolet detector - Google Patents
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1856—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising nitride compounds, e.g. GaN
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- H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type
- H01L31/1085—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type the devices being of the Metal-Semiconductor-Metal [MSM] Schottky barrier type
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Abstract
A manufacturing method of a high-performance self-driven GaN nanowire ultraviolet detector relates to the field of semiconductor photoelectric detection, and comprises the following steps: (1) Polishing the insulating substrate, cleaning and then performing plasma high-temperature nitridation treatment; (2) growing polycrystalline GaN nanowires; (3) Designing an asymmetric interdigital electrode, wherein the two-stage area difference of the asymmetric interdigital electrode is between 0.3 and 5mm 2 The finger spacing between the interdigital electrodes is 50-300 mu m, the finger width is 50-200 mu m, the length of the whole interdigital electrode module is 1-9mm, and the width is 1.5-13mm. (4) The reticle was placed on a GaN sample and cold sputtered. The invention utilizes the preparation of asymmetric electrodes to cause different widths of depletion layers so as to form built-in potential difference, the potential difference is more than 0.1eV, thereby promoting the separation of electron hole pairs and improving the ultraviolet response speed, and the light response time and the recovery time are less than 1ms; the light responsivity is more than 30mW/cm 2 The detection rate is greater than 10 12 Jones。
Description
Technical Field
The present disclosure relates to a high performance self-driven GaN nanowire ultraviolet detector in the field of semiconductor forbidden band light excitation, and more particularly to an asymmetric MSM schottky type photodetector.
Background
With the development of technology, human beings have great interest in exploring light wavelengths beyond 400-700nm, a photodetector is a device capable of absorbing light with specific wavelength and converting photon energy into photocurrent, gallium nitride (GaN) is a typical representative of three-generation semiconductors, the forbidden bandwidth of the gallium nitride (GaN) is 3.4eV, the gallium nitride just corresponds to light excitation with 365nm wavelength, and research on the ultraviolet detection field of gallium nitride is a hotspot of the global semiconductor industry at present, and the gallium nitride has excellent chemical and physical properties such as wide forbidden bandwidth, high carrier mobility, high thermal conductivity, high chemical stability and the like, so that the gallium nitride can be suitable for various application scenes.
The main working principle of the gallium nitride ultraviolet detector is divided into the following steps: firstly, a gallium nitride nanowire absorbs photons with corresponding wavelength (365 nm), and the energy of the photons excites electrons positioned in a valence band to transit to a conduction band to generate electron hole pairs; secondly, separating electron hole pairs under the action of a built-in electric field in the period; and finally collecting carriers at the electrode, and forming current through an external lead.
At present, in a global large environment, high efficiency and low energy consumption are development directions in the field of ultraviolet detection, on one hand, defects formed in the preparation process are mainly reduced, gallium nitride materials with high crystallinity and few defects can be prepared, and more importantly, a proper detector structure is selected, and at present, the ultraviolet detector structure mainly has the following schemes: with structures using pn junctions including p-n type, p-i-n type, and structures using schottky contacts including MIS type, MSM type, etc., most current uv detectors rely on external bias driving to operate, which limits their independence in real-time practical applications. And simultaneously, the power consumption in the working process is increased.
At home and abroad, some researches are carried out on GaN-based ultraviolet detectors, and various structures and heterojunctions are involved, but the preparation process is complex, the detection rate is low, and the comprehensive performance is required to be improved.
Disclosure of Invention
The manufacturing method of the gallium nitride nanowire ultraviolet detector provided by the invention utilizes low-cost MPCVD to prepare the original GaN nanowire, and uses the magnetron sputtering instrument to prepare the asymmetric interdigital electrode by cold sputtering, so that the ultra-high vacuum is avoided in the preparation process of the ultraviolet detector, the overlapping preparation of a plurality of films is avoided, the problems of complicated manufacturing process and complex preparation process of the detector are effectively solved, the excellent detection performance is realized, and an effective way is provided for the large-scale production and application of the gallium nitride nanowire ultraviolet detector.
The preparation method of the GaN ultraviolet detector comprises the following steps:
step one, performing plasma nitridation treatment on a detector insulating substrate material; the detector substrate material is an electric insulating material or the surface of the substrate is an insulating layer, surface plasma nitriding treatment is carried out after organic cleaning, then a catalyst layer is prepared on the substrate after the plasma nitriding treatment by adopting magnetron sputtering, the catalyst is metal, and the thickness of the catalyst layer is 3-10nm.
Step two: preparing a GaN nanowire ultraviolet detection functional film layer; preparing a GaN nanowire film on a substrate of a plasma nitriding treatment and sputtering catalyst, wherein the length of the prepared GaN nanowire is 5-20 mu m, and the diameter of the prepared GaN nanowire is 50-300nm; the method comprises the steps of carrying out a first treatment on the surface of the
Step three: designing and manufacturing an asymmetric electrode mask; the two-stage area difference of the asymmetric interdigital electrode is between 0.3 and 5mm 2 The finger spacing between the interdigital electrodes is 50-300 mu m, the finger width is 50-200 mu m, the length of the whole interdigital electrode module is 1-9mm, and the width is 1.5-13mm;
step four: depositing a metal electrode; sputtering a metal electrode with the thickness of 50-200nm by using a mask;
step five: ageing the device; the irradiation intensity is not less than 5mW/cm 2 Carrying out device irradiation by an ultraviolet light source, and applying voltage of 0.1-5V to carry out device aging treatment, wherein the aging time is not less than 24 hours;
further, in step 1, the substrate is an electrical insulating material or the surface is an insulating layer and plasma thereof is subjected to surface nitriding treatment, the nitriding depth is more than 10nm, and the surface resistivity of the substrate material is more than 10 11 Omega cm; the plasma pretreatment treatment has a treatment temperature of 600-850 ℃ and a plasma density of more than 3 x 10 10 cm -3 Treatment time: 0.5-3h;
further, the preparation of the GaN nanowire functional film layer in the second step adopts plasma equipment and uses N 2 As a nitrogen source.
Further, the asymmetric electrode is designed and manufactured in the step 3, and the asymmetric electrode is constructed by adopting different contact materials and contact areas, so that the contact potential barrier difference between the two ends of the electrode and the GaN nanowire functional film layer is more than 0.1eV;
further, in the fourth step, the electrode material is a metal or semiconductor material with resistivity lower than 5 mu omega cm.
Further, irradiation is used in step 5Intensity of not less than 5mW/cm 2 Carrying out device irradiation by an ultraviolet light source, and applying voltage of 0.1-5V to carry out device aging treatment, wherein the aging time is not less than 24 hours;
after the asymmetric electrode is contacted with the nanowire by utilizing different electrode areas, the work function of the metal electrode is larger than that of the electrode of the GaN nanowire, schottky contact is formed through two sides of electron transfer, meanwhile, the depletion layers with different widths are formed due to different electron numbers transferred by two poles caused by different areas of the metal electrode, so that corresponding built-in potential is generated inside the depletion layers, after the GaN nanowire absorbs ultraviolet photons below 365nm, an excited electron hole pair is formed inside the nanowire, an external electric field is not needed, the self-driving is realized only by separation under the driving of the built-in potential, the electron hole reaches two poles respectively, and the device belongs to an MSM structure, can realize lower dark current by combining the characteristics of a GaN wide band gap semiconductor and can quickly separate photo-generated carriers through built-in potential energy.
The invention has the following advantages and benefits:
A. the invention uses plasma to carry out high-temperature nitriding treatment on the substrate, so that the surface crystal lattice of the substrate releases internal stress, adapts to the environment of high-temperature plasma, reduces the degree of lattice mismatch, and can ensure the crystallinity and stability of the GaN grown in the later stage by using the plasma to etch the pollutants on the surface.
A. The invention utilizes the spontaneous potential difference formed by the interdigital electrodes of the asymmetric index to induce the separation of photo-generated electron hole pairs, thereby forming the self-driven ultraviolet detector.
B. The ultraviolet detector is structurally a photovoltaic detector with an MSM structure, so that the ultraviolet detector has the photoelectric response characteristic of quick response and low dark current.
C. The invention has long-acting property, and the highest response photocurrent attenuation value is less than 5% in one year.
D. The preparation instrument used in the invention is economical and efficient, and the preparation process flow is simple and reliable, thus being applicable to large-scale industrial production.
Description of the drawings:
FIG. 1 is a schematic diagram of a GaN nanowire UV detector
FIG. 2 is a graph showing the ultraviolet absorption cycle of a self-driven ultraviolet detector with a silicon oxide substrate
FIG. 3 is a graph showing the UV absorption cycle of a self-driven UV detector for a sapphire substrate
FIG. 4 is a graph showing the ultraviolet absorption cycle of a self-driven ultraviolet detector with an aluminum nitride substrate
FIG. 5 is a graph showing the cycle of UV absorption by a self-driven UV detector of a silicon carbide substrate
FIG. 6 shows the rise time and fall time of the self-driven UV detector response to 365nm UV light
FIG. 7 is a cycle curve of the stability test of the self-driven ultraviolet detector of example 1
Detailed Description
In order that the manner in which the above recited examples of the invention are obtained will become readily apparent, a more particular description of the invention, briefly summarized below, may be had by reference to the appended drawings and examples, some, but not all of which are illustrated in the appended drawings.
The practical structure of the invention is shown in figure 1, and a top view of an ultraviolet detector with an asymmetric electrode forming a schottky structure is shown in figure, wherein the electrode 1, the GaN nanowire 2 and the insulating substrate 3 are prepared by magnetron sputtering from top to bottom respectively.
Example 1
Step one, polishing the surface of silicon dioxide (SiO 2 ) The substrate is subjected to organic cleaning to remove surface contaminants. Subsequent use of H in MPCVD 2 ,N 2 In a volume ratio of 1:1 surface nitriding treatment for 1h at 15torr and 800 ℃ with microwave power of 300W; the plasma density under this condition was 10 15 cm -3 A nitriding depth of 15nm, and a surface resistivity of 10 after nitriding 15 Ωcm，SiO 2 The crystal orientation is (100), and then an Au catalyst layer of 5nm is magnetically sputtered on the substrate after the plasma nitriding treatment.
Step two, using Microwave Plasma Chemical Vapor Deposition (MPCVD) to use H 2 ,N 2 In a volume ratio of 1:1 a layer of GaN nanowire is catalytically grown on a substrate after plasma nitriding treatment and sputtering catalyst at 15torr and 850 ℃, and the average length of the GaN nanowire is 20 mu m and the diameter is 280nm.
Step three, designing and manufacturing the asymmetric interdigital electrode mask plate with the two polar areas of 1.5mm 2 The finger spacing is 200 mu m, the finger width is 150 mu m, the two pole indexes differ by 1, the length of the whole interdigital electrode module is 6mm, and the width is 8mm.
And fourthly, cold sputtering an interdigital electrode on the GaN nanowire film layer by using a mask plate and a magnetron sputtering instrument, wherein the electrode material is Au, the resistivity is 2.4 mu omega cm, the electrode thickness is 80nm, and the potential difference of two poles of the interdigital electrode is 0.5eV.
Step five, utilizing the irradiation intensity of 8mW/cm 2 The ultraviolet LED of (2) is irradiated, the wavelength of an ultraviolet light source is 365nm, and meanwhile, the ultraviolet light source is irradiated for 12 hours by applying voltage of 0.1V for aging.
The cyclicity test was carried out without applying a voltage, and the ultraviolet absorption cycle curve obtained from the test is shown in fig. 2, and the photocurrent was 25 μa.
Example 2 of the embodiment
Step one, polishing a sapphire (Al) with a surface 2 O 3 ) And (3) carrying out organic cleaning on the growth substrate to remove surface pollutants. Subsequent use of H in MPCVD 2 ,N 2 The volume ratio of the mixed gas is 1:1 surface nitriding treatment for 2 hours at 20torr and 850 ℃, and microwave power is 400W; the plasma density under this condition was 10 17 cm -3 The nitriding depth was 30nm, and the surface resistivity after nitriding was 10 12 And (3) carrying out magnetron sputtering on the substrate subjected to plasma nitridation treatment for a 5nm Au catalyst layer, wherein the crystal orientation of the substrate is (100) omega cm.
Step two, using Microwave Plasma Chemical Vapor Deposition (MPCVD) to use H 2 ,N 2 In a volume ratio of 1:1, a layer of GaN nanowire is catalytically grown on a substrate after plasma nitriding treatment and catalyst sputtering under the condition of 15torr and 850 ℃, and the average length of the GaN nanowire is 13 mu m and the diameter is 200nm.
Step three, designing and manufacturing the asymmetric interdigital electrode mask plate with the two polar area difference of 2mm 2 The finger spacing is 200 mu m, the finger width is 200 mu m, the two pole indexes differ by 1, the length of the whole interdigital electrode module is 6mm, and the width is 8mm.
And fourthly, cold sputtering an interdigital electrode on the GaN nanowire film layer by utilizing a mask plate and a magnetron sputtering instrument, wherein the electrode material is Cu, the resistivity is 1.75 mu omega cm, and the thickness is 80nm. The potential difference between the two poles of the interdigital electrode is 0.45eV.
Step five, utilizing the irradiation intensity of 8mW/cm 2 The ultraviolet LED of (2) is irradiated, the wavelength of an ultraviolet light source is 365nm, and meanwhile, the ultraviolet light source is irradiated for 12 hours by applying voltage of 0.1V for aging.
The cyclicity test was performed without applying a voltage, and the ultraviolet absorption cycle curve obtained from the test is shown in fig. 3, and the photocurrent was 14 μa.
Example 3
And step one, carrying out organic cleaning on the aluminum nitride (AlN) substrate with the polished surface to remove surface pollutants. Subsequent use of H in PECVD 2 ,N 2 The volume ratio of the mixed gas is 1:1, surface nitriding treatment is carried out for 3 hours under the condition that the air pressure is 40pa and the temperature is 850 ℃, and the radio frequency power is 150W; the plasma density under this condition was 10 11 cm -3 A nitriding depth of 10nm, and a surface resistivity of 10 after nitriding 12 The crystal orientation of the AlN substrate is (100) crystal orientation, and then a Pt catalyst layer of 5nm is subjected to magnetron sputtering on the substrate subjected to plasma nitridation treatment.
Step two, using H in a plasma enhanced chemical vapor deposition system (PECVD) 2 ,N 2 The volume ratio of the mixed gas of (1): 1, a layer of GaN nanowire is catalytically grown on a substrate after plasma nitriding treatment and catalyst sputtering under the condition that the air pressure is 40pa and the temperature is 850 ℃, wherein the average length of the GaN nanowire is 10 mu m, and the diameter of the GaN nanowire is 210nm.
Step three, designing and manufacturing the asymmetric interdigital electrode mask plate with the two polar area difference of 3mm 2 The finger spacing is 200 μm, the finger width is 150 μm, the two pole indexes differ by 2, the length of the whole interdigital electrode module is 6mm, and the width is 8mm.
And fourthly, cold sputtering an interdigital electrode on the GaN nanowire film layer by utilizing a mask plate and a magnetron sputtering instrument, wherein the electrode material is Ag, the resistivity is 1.65 mu omega cm, and the thickness of the electrode is 50nm. The potential difference between the two poles of the interdigital electrode is 0.6eV.
Step five, utilizing the irradiation intensity of 8mW/cm 2 The ultraviolet LED of (2) is irradiated, the wavelength of an ultraviolet light source is 365nm, and meanwhile, the voltage of 0.1V is applied to irradiate for 24 hours for aging.
The cyclicity test was performed without applying a voltage, and the ultraviolet absorption cycle curve obtained from the test is shown in fig. 4, and the photocurrent was 6 μa.
Example 4
Cutting a silicon carbide (SiC) substrate with a polished surface, and performing organic cleaning to remove surface pollutants. Subsequent use of H in PECVD 2 ,N 2 The volume ratio of the mixed gas is 1:1, pretreating for 3 hours at the temperature of 850 ℃ under the air pressure of 40pa, wherein the radio frequency power is 150W; the plasma density under this condition was 10 11 cm -3 The nitriding depth was 30nm, and the surface resistivity after nitriding was 10 12 The crystal orientation of the SiC substrate is (100) crystal orientation, and then a Ni catalyst layer of 5nm is magnetically sputtered on the substrate after plasma nitriding treatment.
Step two, using H in a plasma enhanced chemical vapor deposition system (PECVD) 2 ,N 2 The volume ratio of the mixed gas of (1): 1, a layer of GaN nanowire is catalytically grown on a substrate after plasma nitriding treatment and catalyst sputtering under the condition that the air pressure is 40pa and the temperature is 850 ℃, wherein the average length of the GaN nanowire is 20 mu m, and the average diameter of the GaN nanowire is 340nm.
Step three, designing and manufacturing the asymmetric interdigital electrode mask plate with the area difference of 4mm between two electrode surfaces 2 The finger spacing is 200 mu m, the finger width is 200 mu m, the two pole indexes differ by 2, the length of the whole interdigital electrode module is 6mm, and the width is 8mm.
And fourthly, cold sputtering an interdigital electrode on the GaN nanowire film layer by utilizing a mask plate and a magnetron sputtering instrument, wherein the electrode material is Cu, the resistivity is 1.75 mu omega cm, and the thickness of the electrode is 50nm. The potential difference between the two poles of the interdigital electrode is 0.5eV.
Step five, utilizing the irradiation intensity of 8mW/cm 2 The ultraviolet LED of (2) is irradiated, the wavelength of an ultraviolet light source is 365nm, and meanwhile, the voltage of 0.1V is applied to irradiate for 24 hours for aging.
The cyclicity test was performed without applying a voltage, and the ultraviolet absorption cycle curve obtained from the test is shown in fig. 5, and the photocurrent was 42 μa.
The ultraviolet detector prepared through the step is tested through an independently built test system, and the illumination intensity is calibrated by a thorlabs-PM100D illuminometer.
The response speed is limited by 10% -90% of the current change through the test, the used test instrument is a Ji Li 2636B power meter, no bias voltage can be applied in the test process, 4 implementation example response time analysis is as follows, and the rising time and the falling time shown by the graph of FIG. 6 are all less than 1ms; it is required to show that the response curve obtained by the test is reduced due to the reduction of luminous efficiency caused by the heating of the ultraviolet LED, and the phenomenon is calibrated by the radiometer;
the invention has good cycle stability, and FIG. 7 shows that the photo current is basically maintained at 25 mu A when the ultraviolet cycle curve is measured in 0,2,4,6 and 8 months in the embodiment 1, and the average attenuation rate of the photo current is less than 1%/month, so that the device has good stability. The remaining examples have high stability characteristics, which are not repeated here.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any modifications and substitutions easily contemplated by those skilled in the art within the scope of the present invention are intended to be included in the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (5)
1. A manufacturing method of a high-performance self-driven GaN nanowire ultraviolet detector is characterized by comprising the following steps of:
step one: performing plasma nitridation treatment on the insulating substrate material of the detector and preparing a catalyst; the detector substrate material is an electric insulating material or the surface of the substrate is an insulating layer, surface plasma nitriding treatment is carried out after organic cleaning, then a catalyst layer is prepared on the substrate subjected to the plasma nitriding treatment by adopting magnetron sputtering, the catalyst is metal, and the thickness of the catalyst layer is 3-10nm;
step two: preparing a GaN nanowire ultraviolet detection functional film layer; preparing a GaN nanowire film on a substrate of a plasma nitriding treatment and sputtering catalyst, wherein the length of the prepared GaN nanowire is 5-20 mu m, and the diameter of the prepared GaN nanowire is 50-300nm;
step three: designing and manufacturing an asymmetric electrode mask; the two-stage area difference of the asymmetric interdigital electrode is between 0.3 and 5mm 2 The finger spacing between the interdigital electrodes is 50-300 mu m, the finger width is 50-200 mu m, the length of the whole interdigital electrode module is 1-9mm, and the width is 1.5-13mm;
step four: depositing a metal electrode; sputtering a metal electrode with the thickness of 50-200nm on the GaN nanowire film layer by using a mask;
step five: ageing the device; the irradiation intensity is not less than 5mW/cm 2 And (3) irradiating the device by using an ultraviolet light source, and applying a voltage of 0.1-5V to perform ageing treatment on the device, wherein the ageing time is not less than 24 hours.
2. The method for manufacturing the high-performance self-driven GaN nanowire ultraviolet detector, according to claim 1, is characterized in that: in the first step, the substrate is made of an electric insulating material or the surface of the substrate is an insulating layer, plasma surface nitriding treatment is carried out on the substrate, the nitriding depth is more than or equal to 10nm, and the surface resistivity of the substrate material after the plasma nitriding treatment is more than 10 11 Omega cm; the plasma pretreatment treatment has a treatment temperature of 600-850 ℃ and a plasma density of more than 3 x 10 10 cm -3 Treatment time: 0.5-3h.
3. The method for manufacturing the high-performance self-driven GaN nanowire ultraviolet detector, according to claim 1, is characterized in that: in the second step, a plasma device is adopted for preparing the GaN nanowire functional film layer, and N is used 2 As a nitrogen source.
4. The method for manufacturing the high-performance self-driven GaN nanowire ultraviolet detector, according to claim 1, is characterized in that: and step three, designing and manufacturing an asymmetric electrode, and constructing the asymmetric electrode by adopting different contact materials and contact areas, so that the contact potential barrier difference between the two ends of the electrode and the GaN nanowire functional film layer is more than 0.1eV.
5. The method for manufacturing the high-performance self-driven GaN nanowire ultraviolet detector, according to claim 1, is characterized in that: and in the fourth step, the electrode material is a metal or semiconductor material with the resistivity lower than 5 mu omega cm.
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