CN115360235B - Gallium nitride Schottky barrier diode and manufacturing method thereof - Google Patents

Gallium nitride Schottky barrier diode and manufacturing method thereof Download PDF

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CN115360235B
CN115360235B CN202210951099.8A CN202210951099A CN115360235B CN 115360235 B CN115360235 B CN 115360235B CN 202210951099 A CN202210951099 A CN 202210951099A CN 115360235 B CN115360235 B CN 115360235B
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CN115360235A (en
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王霄
赵梓辰
敖金平
李杨
陈治伟
杨毅喆
张志达
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Jiangnan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
    • H01L29/861—Diodes
    • H01L29/872—Schottky diodes
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/47—Schottky barrier electrodes
    • H01L29/475—Schottky barrier electrodes on AIII-BV compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66083—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by variation of the electric current supplied or the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched, e.g. two-terminal devices
    • H01L29/66196—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by variation of the electric current supplied or the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched, e.g. two-terminal devices with an active layer made of a group 13/15 material
    • H01L29/66204—Diodes
    • H01L29/66212—Schottky diodes
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Abstract

The invention discloses a gallium nitride Schottky barrier diode and a manufacturing method thereof, wherein the gallium nitride Schottky barrier diode consists of a substrate, a buffer layer, an n+ GaN epitaxial layer, an n-GaN epitaxial layer, an ohmic electrode, a Schottky electrode and a conductive layer; the substrate, the buffer layer, the n+ GaN epitaxial layer and the n-GaN epitaxial layer are sequentially contacted from bottom to top; the ohmic electrode and the upper surface of the n+ GaN epitaxial layer form ohmic contact; the Schottky electrode and the upper surface of the n-GaN epitaxial layer form Schottky contact; the upper surfaces of the ohmic electrode and the schottky electrode are covered with a conductive layer. The invention adopts nickel nitride formed by plasma nitridation as a Schottky electrode, and has higher stability and lower reverse leakage current.

Description

Gallium nitride Schottky barrier diode and manufacturing method thereof
Technical Field
The invention belongs to the technical field of microelectronics, and particularly relates to a gallium nitride Schottky barrier diode and a manufacturing method thereof.
Background
A Schottky Barrier Diode (SBD) is a low-power-consumption and ultra-high-speed semiconductor device in a rectifying circuit. The high-frequency high-voltage high-current rectifier is widely applied to circuits such as a switch power supply, a frequency converter and the like, and is used as a high-frequency low-voltage high-current rectifier diode, or is used as a rectifier diode and a small-signal detector diode in circuits such as microwave communication and the like. Since the advent of semiconductors, with the requirements of improving the performance of devices and the increase of the difficulty of device manufacturing techniques, third-generation semiconductor materials represented by gallium nitride (GaN) and silicon carbide (SiC) are favored because of having a larger forbidden band width and higher electron mobility, and GaN materials have good electron transfer characteristics, high breakdown voltage and good thermal conductivity at the same time, while GaN-based SBDs have advantages of short reverse recovery time, low switching loss, and the like.
However, the conventional schottky barrier diode has a disadvantage of large reverse leakage current.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
One of the purposes of the present invention is to provide a gallium nitride schottky barrier diode with smaller reverse leakage current and better process compatibility.
In order to solve the technical problems, the invention provides the following technical scheme: a gallium nitride Schottky barrier diode comprises a substrate, a buffer layer, an n+ GaN epitaxial layer, an n-GaN epitaxial layer, an ohmic electrode, a Schottky electrode and a conductive layer; the substrate, the buffer layer, the n+ GaN epitaxial layer and the n-GaN epitaxial layer are sequentially contacted from bottom to top;
the ohmic electrode and the upper surface of the n+ GaN epitaxial layer form ohmic contact;
the Schottky electrode and the upper surface of the n-GaN epitaxial layer form Schottky contact;
the upper surfaces of the ohmic electrode and the schottky electrode are covered with a conductive layer.
As a preferred embodiment of the gallium nitride schottky barrier diode of the present invention, wherein: the substrate material comprises one of silicon, sapphire, silicon carbide, and homogenous gallium nitride.
As a preferred embodiment of the gallium nitride schottky barrier diode of the present invention, wherein: the thickness of the buffer layer is 1-500 nm. And growing a buffer layer on the substrate by adopting MOCVD (metal organic chemical vapor deposition), MBE (molecular beam epitaxy) and HVPE (high-temperature plasma enhanced vapor deposition) technologies, wherein the buffer layer is preferably a common low-temperature GaN layer or a III-V compound such as a C-doped AlGaN buffer layer.
As a preferred embodiment of the gallium nitride schottky barrier diode of the present invention, wherein: the doping concentration of the n-GaN epitaxial layer is 1 multiplied by 10 16 ～1×10 18 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The doping concentration of the n+ GaN epitaxial layer is 1 multiplied by 10 18 ～1×10 20 cm -3 . The n+ GaN epitaxial layer and the n-GaN epitaxial layer are grown by MOCVD process.
As a preferred embodiment of the gallium nitride schottky barrier diode of the present invention, wherein: the thickness of the ohmic electrode is 40-3000 nm; the ohmic electrode is made of titanium, aluminum, titanium and gold in sequence from bottom to top, and the titanium layer and the n+ GaN epitaxial layer form ohmic contact; the thicknesses of the titanium layer, the aluminum layer, the titanium layer and the gold layer are respectively 5-400 nm, 20-1000 nm, 10-900 nm and 5-700 nm; the conducting layer is made of titanium and gold, and the thicknesses of the titanium and the gold are 40nm and 50nm respectively.
As a preferred embodiment of the gallium nitride schottky barrier diode of the present invention, wherein: the thickness of the Schottky electrode is 1-100 nm; the material of the Schottky electrode is nickel nitride, the Schottky electrode is prepared by nitriding nickel metal through nitrogen plasma, and the nickel nitride and the n-GaN epitaxial layer form Schottky barrier contact.
As a preferred embodiment of the gallium nitride schottky barrier diode of the present invention, wherein: a space of 0.01-100 μm is arranged between the ohmic electrode and the Schottky electrode; the preferred pitch is 1 μm.
Another object of the present invention is to provide a method for manufacturing a gallium nitride schottky barrier diode according to any one of the above, comprising:
growing a buffer layer on the substrate, and growing an n+ GaN epitaxial layer and an n-GaN epitaxial layer on the buffer layer;
performing mesa etching on the n-GaN epitaxial layer to expose a part of the area of the n+ GaN layer;
sequentially depositing a titanium layer, an aluminum layer, a titanium layer and a gold layer on the exposed n+ GaN epitaxial layer, and performing thermal annealing treatment in a nitrogen atmosphere to form an ohmic electrode;
firstly, performing magnetron sputtering to deposit a layer of nickel on the n-GaN epitaxial layer, and then nitriding by using nitrogen plasma to generate nickel nitride, so as to form a Schottky electrode;
a conductive layer is deposited over the ohmic electrode and the schottky electrode.
As a preferable embodiment of the method for manufacturing a gallium nitride schottky barrier diode of the present invention, wherein: and a layer of nickel is firstly deposited on the n-GaN epitaxial layer by magnetron sputtering, and the deposition thickness is 1-100 nm.
As a preferable embodiment of the method for manufacturing a gallium nitride schottky barrier diode of the present invention, wherein: the nitrogen plasma is used for nitriding to generate nickel nitride, the power of the introduced plasma is 10-200W, the plasma pressure is 0.2-10 mTorr, and the reaction time is 1-500 s; preferably, the power of the introduced plasma is 100W, the plasma pressure is 2mTorr, and the reaction time is 90s.
Compared with the prior art, the invention has the following beneficial effects:
the diode provided by the invention adopts the nickel nitride nitrided by the plasma as the Schottky electrode material, has higher stability and lower reverse leakage current, and can effectively reduce the power consumption of the device and improve the efficiency of the device compared with the device manufactured by the traditional method.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a schematic diagram of a GaN Schottky barrier diode of the present invention;
FIG. 2 is an I-V test curve of a nickel nitride Schottky barrier diode and a Ni Schottky barrier diode of the present invention at different processing times.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
As shown in fig. 1, a gallium nitride schottky barrier diode provided in this embodiment 1 is composed of a substrate 100, a buffer layer 200, an n+ GaN epitaxial layer 300, an n-GaN epitaxial layer 400, an ohmic electrode 500, a schottky electrode 600 and a conductive layer 700; wherein, the substrate 100, the buffer layer 200, the n+ GaN epitaxial layer 300 and the n-GaN epitaxial layer 400 are contacted from bottom to top in sequence;
the n-GaN epitaxial layer 400 does not completely cover the n+ GaN epitaxial layer 300, thereby exposing a portion of the upper surface of the n+ GaN epitaxial layer 300;
ohmic electrode 500 forms ohmic contact with the upper surface of the exposed n+ GaN epitaxial layer 300; the ohmic electrode 500 is sequentially made of titanium, aluminum, titanium and gold from the upper surface of the n+ GaN epitaxial layer 300;
the schottky electrode 600 forms schottky contact with the upper surface of the n-GaN epitaxial layer 400, and the contact material of the schottky electrode 600 is nickel nitride;
the upper surfaces of the ohmic electrode 500 and the schottky electrode 600 are covered with a conductive layer 700, and the conductive layer 700 is made of titanium and gold.
The specific manufacturing process of the gallium nitride Schottky barrier diode comprises the following steps:
(1) A sapphire substrate is adopted, a GaN buffer layer grows on the substrate by adopting an MOCVD technology, and the thickness of the buffer layer is 100nm;
(2) Growing an n+ GaN epitaxial layer on the GaN buffer layer by using an MOCVD process, and growing an n-GaN epitaxial layer on the n+ GaN epitaxial layer; the doping concentration of the n-GaN epitaxial layer is 1 x 10 17 cm -3 The doping concentration of the n+ GaN epitaxial layer is 1 x 10 19 cm -3 ；
(3) Immersing the n-GaN epitaxial layer in deionized water after the n-GaN epitaxial layer is grown, cleaning the surface, and drying the surface by nitrogen after the n-GaN epitaxial layer is washed cleanly;
(4) Etching the n-GaN epitaxial layer by using an inductively coupled plasma etching machine to expose a part of the n+ GaN epitaxial layer;
(5) Sequentially depositing a titanium layer, an aluminum layer, a titanium layer and a gold layer on the exposed n+ GaN epitaxial layer by using a Ti/Al/Ti/Au alloy technology; the thicknesses of the titanium layer, the aluminum layer, the titanium layer and the gold layer are respectively 100nm, 500nm, 250nm and 150nm; the thickness of the ohmic electrode is 1000nm;
(6) Then annealing is carried out in a Rapid Thermal Annealing (RTA) process in a nitrogen atmosphere, and ohmic contact is generated;
(7) Depositing nickel with the thickness of 10nm in a Schottky electrode area through magnetron sputtering, and then nitriding by nitrogen plasma to generate nickel nitride, so that a Schottky electrode is formed, and the distance between an ohmic electrode and the Schottky electrode is 1 mu m; wherein the power of the introduced plasma is 100W, the pressure of the plasma is 2mTorr, and the reaction time is 1.5min;
(8) The upper surfaces of the ohmic electrode and the Schottky electrode are covered with conductive layers of titanium and gold which are deposited by electron beam evaporation or magnetron sputtering, and the thicknesses of the conductive layers are 40nm and 50nm respectively.
Example 2
The overall structure of this embodiment 2 is the same as that of embodiment 1, and is the structure shown in fig. 1. This example 2 differs from example 1 in that the plasma reaction time in step (7) was 1min.
Example 3
The overall structure of this embodiment 3 is the same as that of embodiment 1, and is the structure shown in fig. 1. This example 3 differs from example 1 in that the plasma reaction time in step (7) was 3.5min.
Comparative example 1
The overall structure of this comparative example 1 was the same as that of example 1, and was the same as that shown in fig. 1. This comparative example 1 differs from example 1 in that the schottky anode material is metallic nickel.
The specific manufacturing process of the gallium nitride schottky barrier diode of the present comparative example 1 is:
(1) A sapphire substrate is adopted, a GaN buffer layer grows on the substrate by adopting an MOCVD technology, and the thickness of the buffer layer is 100nm;
(2) Growing an n+ GaN epitaxial layer on the GaN buffer layer by using an MOCVD process, and growing an n-GaN epitaxial layer on the n+ GaN epitaxial layer; the doping concentration of the n-GaN epitaxial layer is 1 x 10 17 cm -3 The doping concentration of the n+ GaN epitaxial layer is 1 x 10 19 cm -3 ；
(3) Immersing the n-GaN epitaxial layer in deionized water after the n-GaN epitaxial layer is grown, cleaning the surface, and drying the surface by nitrogen after the n-GaN epitaxial layer is washed cleanly;
(4) Etching the n-GaN epitaxial layer by using an inductively coupled plasma etching machine to expose a part of the n+ GaN epitaxial layer;
(5) Depositing a titanium layer, an aluminum layer, a titanium layer and a gold layer on the exposed n+ GaN epitaxial layer by using a Ti/Al/Ti/Au alloy technology; the thicknesses of the titanium layer, the aluminum layer, the titanium layer and the gold layer are respectively 100nm, 500nm, 250nm and 150nm; the thickness of the ohmic electrode is 1000nm;
(6) Then annealing is carried out in a Rapid Thermal Annealing (RTA) process in a nitrogen atmosphere to form ohmic contact;
(7) Nickel with the thickness of 10nm is firstly deposited in the Schottky electrode area through magnetron sputtering, nitrogen plasma treatment is not carried out, the Schottky electrode is directly formed, and the distance between the ohmic electrode and the Schottky electrode is 1 mu m;
(8) The upper surfaces of the ohmic electrode and the Schottky electrode are covered with conductive layers of titanium and gold which are deposited by electron beam evaporation or magnetron sputtering, and the thicknesses of the conductive layers are 40nm and 50nm respectively.
The gallium nitride schottky barrier diodes obtained in examples 1 to 3 and comparative example 1 were subjected to performance test, and the test results are shown in fig. 2.
From comparative examples 1 to 3 and comparative example 1, it was found that reverse leakage was maximum when Ni was used as a schottky electrode in comparative example 1, and was minimum when the plasma treatment time was increased (from comparative example 1 to example 2, to example 1, to example 3), and the reverse leakage was decreased first and then increased, and was minimum in example 1 having a treatment time of 1.5min; while the threshold voltage in the forward direction was the smallest in comparative example 1, the threshold voltage was always increased with the increase in the processing time, and the threshold voltage was the largest in example 3, but the overall difference was not large. In short, the reverse leakage of the Schottky diode of the nickel nitride electrode treated by the nitrogen plasma is obviously reduced compared with that of the Ni electrode, and the minimum is reached at the optimal treatment time of 1.5 min.
The diode provided by the invention adopts the nickel nitride nitrided by the plasma as the Schottky electrode, has higher stability and lower reverse leakage current, and can effectively reduce the power consumption of the device and improve the efficiency of the device compared with the device manufactured by the traditional method.
The mesa structure diode has good process compatibility, can have larger size according to actual requirements, can meet the requirements of high breakdown voltage and low leakage current, and has wider application range.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.

Claims (4)

1. A preparation method of a gallium nitride Schottky barrier diode is characterized in that: the method comprises the steps of growing a buffer layer on a substrate, and growing an n+ GaN epitaxial layer and an n-GaN epitaxial layer on the buffer layer;
performing mesa etching on the n-GaN epitaxial layer to expose a part of the area of the n+ GaN layer;
sequentially depositing a titanium layer, an aluminum layer, a titanium layer and a gold layer on the exposed n+ GaN epitaxial layer, and performing thermal annealing treatment in a nitrogen atmosphere to form an ohmic electrode;
firstly, performing magnetron sputtering to deposit a layer of nickel on the n-GaN epitaxial layer, then performing nitridation by using nitrogen plasma to generate nickel nitride, introducing plasma with the power of 100W and the plasma pressure of 2mTorr and the reaction time of 90s to form a Schottky electrode;
the ohmic electrode and the schottky electrode were spaced apart by 1 μm and a conductive layer was deposited over the ohmic electrode and the schottky electrode.
2. The gallium nitride schottky barrier diode according to claim 1, wherein: the thickness of the Schottky electrode is 1-100 nm.
3. The gallium nitride schottky barrier diode according to claim 1, wherein: the ohmic electrode is made of titanium, aluminum, titanium and gold in sequence from bottom to top, and the titanium layer and the n+ GaN epitaxial layer form ohmic contact;
the thickness of the ohmic electrode is 40-3000 nm;
the thickness of the buffer layer is 1-500 nm;
the doping concentration of the n-GaN epitaxial layer is 1 multiplied by 10 16 ～1×10 18 cm -3 The said
The doping concentration of the n+ GaN epitaxial layer is 1 multiplied by 10 18 ～1×10 20 cm -3 ；
The conducting layer is made of titanium and gold;
the substrate material comprises one of silicon, sapphire, silicon carbide, and homogenous gallium nitride.
4. The gallium nitride schottky barrier diode according to claim 1, wherein: and a layer of nickel is firstly deposited on the n-GaN epitaxial layer by magnetron sputtering, and the deposition thickness is 1-100 nm.
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CN114335169A (en) * 2021-11-25 2022-04-12 江西誉鸿锦材料科技有限公司 Gallium nitride Schottky barrier diode and manufacturing method thereof
CN115763247B (en) * 2023-02-13 2023-06-06 江苏能华微电子科技发展有限公司 GaN Schottky barrier diode with quasi-vertical structure and preparation method thereof

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