CN108493290B - Ultraviolet light response device and preparation method thereof - Google Patents

Ultraviolet light response device and preparation method thereof Download PDF

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CN108493290B
CN108493290B CN201810398413.8A CN201810398413A CN108493290B CN 108493290 B CN108493290 B CN 108493290B CN 201810398413 A CN201810398413 A CN 201810398413A CN 108493290 B CN108493290 B CN 108493290B
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CN108493290A (en
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于乃森
陈向丰
齐岩
赵海燕
董大朋
苑青
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Dalian Minzu University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/08Semiconductor 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
    • H01L31/10Semiconductor 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
    • H01L31/101Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/109Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN heterojunction type
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    • H01L31/00Semiconductor 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
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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

Ultraviolet light response device and preparation method thereof
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.
CN201810398413.8A 2018-04-28 2018-04-28 Ultraviolet light response device and preparation method thereof Expired - Fee Related CN108493290B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270471A (en) * 2008-05-16 2008-09-24 南京大学 Method for growing nonpolar face GaN thin-film material and uses thereof
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270471A (en) * 2008-05-16 2008-09-24 南京大学 Method for growing nonpolar face GaN thin-film material and uses thereof
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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