CN108493290B - Ultraviolet light response device and preparation method thereof - Google Patents
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- 230000004298 light response Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 54
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 47
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical group [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 13
- 239000010980 sapphire Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 11
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011654 magnesium acetate Substances 0.000 claims abstract description 8
- 235000011285 magnesium acetate Nutrition 0.000 claims abstract description 8
- 229940069446 magnesium acetate Drugs 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005699 Stark effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—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 in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
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Abstract
An ultraviolet light response device based on a MgO nano material/A-surface gallium nitride structure is characterized in that a MgO nano material/A-surface GaN based core-shell array structure layer is arranged between an R-surface sapphire substrate and a front transparent contact electrode, and a low-temperature GaN buffer layer, an A-surface GaN epitaxial layer film, a magnesium oxide/gallium oxide composite seed crystal layer and a MgO nano material layer are sequentially arranged on the core-shell array structure layer from the R-surface sapphire substrate to the front transparent contact electrode. The invention takes R-surface sapphire as a substrate, an A-GaN structure layer of the R-surface sapphire is obtained by growing a low-temperature GaN buffer layer and an A-GaN epitaxial layer in sequence by adopting a low-pressure organic chemical vapor deposition method, and a nano MgO structure layer is obtained by growing a magnesium oxide precursor structure and heating by adopting magnesium acetate and hexamethylenetetramine as raw materials. The preparation method is simple, the reaction temperature is low, and the prepared product has very good photoresponse to ultraviolet light of 300-400nm, and particularly has very high photoresponse speed.
Description
Technical Field
The invention relates to a photoelectric detector and a preparation method thereof.
Background
Gallium nitride (GaN) is an important wide bandgap semiconductor material, and has good photoelectric properties, and zinc oxide has been the focus of research for the long time due to its excellent optical and electrical properties. At present, most devices are manufactured on polar c-plane (0001) GaN-based materials, and quantum Stark effect exists. Affecting the optoelectronic properties of the device. The nonpolar GaN-based device can eliminate a built-in electric field generated by a polarization effect, overcome the problem of electron hole space separation and improve the luminous efficiency of the device. But the p-type nonpolar GaN material with high hole concentration and high quality is obtained, and the development of the nonpolar GaN-based ultraviolet detector is seriously restricted.
In addition, as an important nano metal oxide material, the MgO material has many excellent properties such as good chemical stability and thermal stability, and is commonly used as a buffer layer between some functional oxide thin film materials and a semiconductor substrate, so that the lattice mismatch between the functional oxide thin film materials and the semiconductor substrate is effectively relieved, the diffusion phenomenon is prevented, and the MgO material has a wide application prospect in the field of micro electronic components. Meanwhile, MgO is a wide-bandgap semiconductor, the bandgap width of which is as high as 7.8eV, and can effectively block electrons and passivate the surface defects of the material.
Disclosure of Invention
The invention aims to provide an ultraviolet light response device based on an MgO nano material/A-surface gallium nitride structure and a preparation method thereof, wherein the ultraviolet light response device is simple in preparation process, low in cost, excellent in performance and stable.
The invention mainly adopts nano magnesium oxide as an electron blocking layer to construct an ultraviolet detector based on MgO nano material/A-plane gallium nitride. The A-GaN structure layer adopts a low-pressure organic chemical vapor deposition (MOCVD) method to grow the low-temperature GaN buffer layer and the A-GaN epitaxial layer in sequence, and the nanometer MgO structure layer adopts magnesium acetate and hexamethylenetetramine as raw materials to grow an MgO precursor structure and is heated to obtain the MgO nanometer structure.
The ultraviolet response device based on the MgO nano material/A-surface gallium nitride structure is characterized in that a MgO nano material/A-surface GaN-based core-shell array structure layer is arranged between an R-surface sapphire substrate and a front transparent contact electrode, and the core-shell array structure layer is sequentially provided with a low-temperature GaN buffer layer, an A-surface GaN epitaxial layer film, a magnesium oxide/gallium oxide composite seed crystal layer and an MgO nano material layer from the R-surface sapphire substrate to the front transparent contact electrode. In the MgO nano material/A surface GaN core-shell array based structure layer, the thickness of the low-temperature GaN buffer layer is 50nm, the thickness of the A surface GaN epitaxial layer film is 1 mu m, the thickness of the magnesium oxide/gallium oxide composite seed crystal layer is 10-20nm, and the thickness of the MgO nano material layer is 100-200 nm. The transparent contact electrode is ITO conductive glass engraved with a channel of 0.1 cm.
Secondly, the preparation method of the ultraviolet light response device comprises the following steps:
① the method comprises preparing sapphire with R surface as substrate by low pressure organic chemical vapor depositionThe growth temperature of the low-temperature GaN buffer layer is 550 ℃, and then TMGa is used as a gallium source and NH is used as a low-pressure organic chemical vapor deposition method3As an N source, the growth temperature is 1000 ℃ to grow the A-GaN epitaxial layer.
②, placing the A-plane GaN grown in the step ① in an annealing furnace, rapidly annealing at 1000 ℃ for 10 minutes in an oxygen atmosphere, and naturally cooling to grow a gallium oxide layer on the surface of the GaN.
③ dissolving 50mM magnesium acetate in absolute ethyl alcohol to obtain seed crystal solution, placing the substrate processed in step ② on a spin coater, dripping the seed crystal solution on the surface, standing for 5 minutes, performing spin coating at the rotation speed of 2500 rpm for 5 minutes, placing the substrate with the seed crystal on a rapid heating table, rapidly heating at 200 ℃ for 15 minutes, and naturally cooling to room temperature to obtain the magnesium oxide/gallium oxide composite seed crystal layer.
④ dissolving 1.1g magnesium acetate and 0.70g hexamethylenetetramine in 100mL water, stirring rapidly to obtain a mixed solution, immersing the substrate with composite seed crystal growth processed in step ③ in the mixed reaction solution, reacting at 90 ℃ for 5 hours, taking out the obtained substrate after the reaction is finished, washing with water, and drying to obtain a magnesium hydroxide precursor layer attached to the substrate.
⑤ placing the substrate processed in step ④ in a heating furnace to heat to 400 ℃ at the heating rate of 10 ℃/minute, preserving the heat for 1 hour, and naturally cooling to room temperature to obtain the magnesium oxide nano flaky layer.
⑥ ITO conductive glass with 0.1cm channel is adhered to the surface of the core-shell array structure processed in step ⑤ and fixed, so as to construct a simple ultraviolet light response device.
Compared with the prior art, the invention has the following advantages:
1. the product of the invention has very good photoresponse to ultraviolet light (UV-A wave band), has quick response time, and overcomes the defect of slow reaction caused by continuous photoconduction of the existing gallium nitride-based ultraviolet detector.
2. The preparation method of the invention does not need a catalyst, has good repeatability, simple process operation and low manufacturing cost.
Drawings
FIG. 1 is a schematic diagram of a structure and a test model of an ultraviolet light response device based on a nano MgO/A-plane GaN structure in an embodiment of the invention;
FIG. 2 is a scanning electron microscope topography of a MgO nano-sheet structure grown on the surface of an A-side GaN film in an embodiment of the invention;
FIG. 3 is an I-V curve under the dark state and ultraviolet illumination of the fast ultraviolet light response device based on the MgO/A-plane GaN structure in the embodiment of the present invention;
FIG. 4 is a graph showing the time-dependent current variation under illumination of an inverted fast ultraviolet light response device based on a nano MgO/A-plane GaN structure in an embodiment of the present invention;
FIG. 5 is a graph showing a single period of current change over time for a fast UV-responsive device based on a nano MgO/A-plane GaN structure according to an embodiment of the present invention (FIG. a), a rising current of an UV lamp on (FIG. b), and a falling current of the UV lamp off (FIG. c).
Description of the above figures
As can be seen from FIG. 1, the ultraviolet light response device based on the nano MgO/A-plane GaN structure has a simple structure, and the nano MgO/A-plane GaN structure layer is arranged between the sapphire substrate 1 and the glass surface 7 evaporated transparent contact electrode 6. Wherein, the transparent contact electrode is ITO conductive glass with a channel of 0.1 cm; the GaN structure layer based on the nanometer MgO/A surface sequentially comprises a low-temperature GaN buffer layer 2, an A surface GaN epitaxial layer film 3, a gallium oxide and MgO composite seed crystal layer 4 and an MgO nanometer flaky layer 5 growing on the surface of the composite seed crystal layer from top to bottom. In the test process, the contact electrode is fixed with the sample, externally connected with 5V bias voltage and connected with an ammeter for photoresponse test. Wherein the light source is 365nm ultraviolet light source, and the optical power density is 300mW/cm2。
As can be seen from FIG. 2, the surface of the A-GaN epitaxial thin film is uniformly coated with MgO nano-platelets.
As can be seen from FIG. 3, the nano MgO/A-GaN ultraviolet detector prepared by the embodiment of the invention has very good photoresponse to ultraviolet light (365nm), and the photocurrent of the ultraviolet detector is remarkably improved under the irradiation of an ultraviolet lamp.
As can be seen from FIG. 4, the nano MgO/A-GaN ultraviolet detector prepared by the embodiment of the invention has good stability, and the photocurrent shows periodic response with the periodic switching of the ultraviolet lamp.
As can be seen from fig. 5, the nano MgO/a-GaN uv detector prepared according to the embodiment of the present invention responds to photocurrent particularly rapidly in a test period, and as can be seen from the amplified rising (uv lamp on) and falling (uv lamp off) processes, the device has very fast uv response characteristics, and the photocurrent rising and falling time is 0.05 seconds.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Examples
Taking an R-surface sapphire as a substrate, firstly, taking H as2Heating at 1150 deg.C for 10min under atmosphere to remove oxide film on the surface of the substrate. Growing by using a low-pressure organic chemical vapor deposition Method (MOCVD), and then reducing the temperature to 550 ℃ to grow a low-temperature GaN buffer layer with the thickness of 50 nm. Then TMGa is used as gallium source and NH is used3As an N source, an A-GaN epitaxial layer film with the growth temperature of 1000 ℃ is grown with the thickness of 1.5 mu m. And placing the grown GaN with the A surface in an annealing furnace, rapidly annealing for 10 minutes in an oxygen atmosphere, and naturally cooling to grow a gallium oxide layer on the surface of the GaN. Then preparing a seed crystal solution, and dissolving 50mM magnesium acetate in absolute ethyl alcohol to prepare the seed crystal solution; placing the grown A-surface GaN substrate on a spin coater, dripping a seed crystal solution on the surface, standing for 5 minutes, performing spin coating at a rotating speed of 2500 rpm for 5 minutes, then placing the substrate with the grown seed crystal on a rapid heating table, rapidly heating at 200 ℃ for 15 minutes, and then naturally cooling to room temperature; and preparing the magnesium oxide/gallium oxide composite seed crystal layer with the thickness of 10-20 nm. Dissolving 1.1g of magnesium acetate and 0.70g of hexamethylenetetramine in 100ml of water, and quickly and uniformly stirring to prepare a mixed solution; immersing the substrate with the seed crystal grown after the heat treatment into the mixed solutionThe reaction was carried out at 90 ℃ for 5 hours. And after the reaction is finished, taking out the obtained substrate, washing with water, and airing to obtain a magnesium hydroxide precursor layer attached to the substrate. And the substrate is placed in a heating furnace to be heated to 400 ℃ at the heating rate of 10 ℃/min, and naturally cooled to room temperature after being kept for 1 hour, so as to prepare the magnesium oxide nano flaky layer with the thickness of 100-200 nm. And finally, attaching the ITO conductive glass etched with the channel of 0.1cm to the surface of the magnesium oxide nanosheet layer of the obtained core-shell array, and fixing to obtain the ultraviolet light response device based on the magnesium oxide/A-surface gallium nitride structure, wherein the structure of the ultraviolet light response device is shown in figure 1, and a MgO-based nanomaterial/A-surface GaN structure layer is arranged between the R-surface sapphire substrate 1 and the glass surface 7 evaporation-coated transparent contact electrode 6. Wherein, the transparent contact electrode is ITO conductive glass with a channel of 0.1 cm; the MgO/A surface GaN structure layer is composed of a GaN low-temperature buffer layer 2, an A surface GaN epitaxial layer 3, a gallium oxide/MgO composite seed crystal layer 4 and a MgO nano flaky layer 5 growing on the surface of the seed crystal layer from top to bottom in sequence.
Claims (4)
1. An ultraviolet light response device based on MgO nano material/A-surface gallium nitride structure is characterized in that: a MgO nano material/A surface GaN based core-shell array structure layer is arranged between an R surface sapphire substrate and a front transparent contact electrode, and a low-temperature GaN buffer layer, an A surface GaN epitaxial layer film, a magnesium oxide/gallium oxide composite seed crystal layer and a MgO nano material layer are sequentially arranged on the core-shell array structure layer from the R surface sapphire substrate to the front transparent contact electrode.
2. The ultraviolet-responsive device of MgO nanomaterial/a-plane gallium nitride structure of claim 1, wherein: in the MgO nano material/A surface GaN core-shell array structure layer, the thickness of the low-temperature GaN buffer layer is 50nm, the thickness of the A surface GaN epitaxial layer film is 1-1.5 mu m, the thickness of the magnesium oxide/gallium oxide composite seed crystal layer is 10-20nm, and the thickness of the MgO nano material layer is 100-200 nm.
3. The ultraviolet-responsive device of MgO nanomaterial/a-plane gallium nitride structure of claim 1, wherein: the transparent contact electrode is ITO conductive glass engraved with a channel of 0.1 cm.
4. The method for preparing an ultraviolet-responsive device of MgO/A-side gallium nitride structure according to claim 1, characterized in that:
① the method comprises growing low-temperature GaN buffer layer by low-pressure organic chemical vapor deposition at 550 deg.C on R-surface sapphire substrate, and then adopting low-pressure organic chemical vapor deposition with TMGa as gallium source and NH3As N source, growing A-GaN epitaxial layer at 1000 deg.C;
②, placing the A-surface GaN grown in the step ① in an annealing furnace, rapidly annealing at 1000 ℃ for 10 minutes in an oxygen atmosphere, and naturally cooling;
③ dissolving 50mM magnesium acetate in absolute ethyl alcohol to obtain seed crystal solution, placing the substrate processed in step ② on a spin coater, dripping the seed crystal solution on the surface, standing for 5min, performing spin coating at 2500 rpm for 5min, placing the substrate with the seed crystal on a rapid heating table, rapidly heating at 200 deg.C for 15 min, and naturally cooling to room temperature;
④ dissolving 1.1g of magnesium acetate and 0.70g of hexamethylenetetramine in 100mL of water, rapidly and uniformly stirring to prepare a mixed solution, immersing the substrate which is processed in the step ③ and is grown with the composite seed crystal into the mixed reaction solution, reacting for 5 hours at 90 ℃, taking out the obtained substrate after the reaction is finished, washing with water, and drying in the air;
⑤, placing the substrate processed in step ④ in a heating furnace, heating to 400 ℃ at the heating rate of 10 ℃/minute, preserving heat for 1 hour, and naturally cooling to room temperature;
⑥ ITO conductive glass with 0.1cm channel is adhered to the surface of the core-shell array structure processed in step ⑤ and fixed.
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| CN101527314A (en) * | 2009-03-19 | 2009-09-09 | 电子科技大学 | ABO3/MgO/GaN heterojunction structure and preparation method thereof |
| CN106549079A (en) * | 2016-09-30 | 2017-03-29 | 大连民族大学 | A kind of ultraviolet light detector and preparation method thereof |
| CN107275424A (en) * | 2017-06-13 | 2017-10-20 | 大连民族大学 | A kind of ultraviolet light response device and preparation method based on homogeneity ZnO nano nucleocapsid array |
| CN107799624A (en) * | 2017-09-08 | 2018-03-13 | 大连民族大学 | One kind is based on the inversion type rapid ultraviolet photoresponse device and preparation method of nano NiO/AlGaN heterojunction structures |
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