CN116741625A - Ion implantation-based p-type polycrystalline beta-Ga 2 O 3 Preparation method and application of film - Google Patents

Ion implantation-based p-type polycrystalline beta-Ga 2 O 3 Preparation method and application of film Download PDF

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CN116741625A
CN116741625A CN202310949190.0A CN202310949190A CN116741625A CN 116741625 A CN116741625 A CN 116741625A CN 202310949190 A CN202310949190 A CN 202310949190A CN 116741625 A CN116741625 A CN 116741625A
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film
beta
type polycrystalline
preparation
ion implantation
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施倩倩
韦素芬
李明逵
柴智
陈涛
吴梦春
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Xiamen Xinsiwang Integrated Circuit Technology Co ltd
Jimei University
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Xiamen Xinsiwang Integrated Circuit Technology Co ltd
Jimei University
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Abstract

The invention discloses a p-type polycrystal beta-Ga based on ion implantation 2 O 3 The preparation method of the film comprises the steps of injecting oxygen positive ions with ultra-large dosage at high energy, and enabling O to be in the ion injection depth: the atomic ratio of Ga is greater than or equal to beta-Ga 2 O 3 An ideal atomic ratio of 1.5, and forming an amorphous or polycrystalline compound of gallium oxynitride Ga-O-N; after ion implantation, high temperature thermal annealing is performed to convert amorphous or polycrystalline compounds of gallium oxynitride Ga-O-N into N-doped p-type polycrystalline beta-Ga 2 O 3 The film is applied to an ultraviolet photoelectric detector. The p-type polycrystal beta-Ga prepared by the invention 2 O 3 The film has better P-type electrical property, and the concentration of hole carriers reaches 10 18 cm ‑3 The order of magnitude of (c) improves the performance of the application device.

Description

Ion implantation-based p-type polycrystalline beta-Ga 2 O 3 Preparation method and application of film
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to p-type polycrystalline beta-Ga based on ion implantation 2 O 3 A preparation method and application of the film.
Background
Gallium oxide is a typical direct bandgap semiconductor material having five phases of α, β, γ, δ, ε, wherein β -Ga 2 O 3 The material and chemical properties are the most stable, the forbidden bandwidth is 4.9eV, and the breakdown field strength is 8MV cm -1 Is a transparent conductive oxide material with very good application prospect, and can be applied to: high power electronics, kilovolt schottky barrier diodes, enhancement mode and depletion mode high voltage high power MOSFETs and MESFETs, deep ultraviolet photodetectors, light emitting diodes, sensors, solar cells, photocatalysts, phosphors, and the like.
Preparation of high quality beta-Ga with high carrier concentration, low resistivity and good mobility 2 O 3 Thin films are critical for device applications. For realizing n-type beta-Ga 2 O 3 For all that is, alreadyGood research results are achieved, and n-type beta-Ga has been successfully prepared by doping IV group elements (such as Si, ge and Sn) and transition metals (such as Nb, zr and Ta) 2 O 3 Film with electron carrier concentration of 10 16 To 10 19 cm -3 At maximum, can approach 10 20 cm -3 。
In comparison with n-type, in Ga 2 O 3 The effective p-type doping is still in the phase of searching for suitable acceptor impurities to obtain better p-type electrical properties. beta-Ga of the prior art 2 O 3 Mainly comprising the following two directions:
1. metal elements such as Cu, zn, mg and the like are doped to replace Ga. The valence electrons of Cu, zn and Mg are less than that of Ga, and when impurity atoms and gallium atoms form covalent bonds, holes are left in the covalent bonds due to the lack of valence electrons, so that p-type is formed. However, doping of Cu, zn, mg, and other metal elements results in a thin film with a smaller band gap, which is related to the introduction of impurity level and grain size change after doping. The increase of metal impurity atoms promotes the recombination of electrons and holes so as to change the photoluminescence performance of the film, and has influence on the band gap of the material, thereby influencing the optical performance of the film. More importantly, the p-type electric property after doping is weaker and is in a high-resistance state.
2. Substitution of nitrogen (N) for beta-Ga 2 O 3 Oxygen (O) in (a) acts as an acceptor impurity, and the atomic radius of N is closest to O, but the valence electron is one less than O, and the 2p orbital energy is higher than O. After N doping, a shallow acceptor impurity level is introduced at the top of the valence band. At present, successful researches are carried out, and high-temperature oxidation of GaN is carried out by adopting oxygen or laughing gas to obtain N-doped p-type beta-Ga 2 O 3 Thin films, but the hole carrier concentration obtained can only reach up to 10 17 cm -3 On this order of magnitude, further breakthroughs are difficult.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a p-type polycrystalline beta-Ga based on ion implantation 2 O 3 A preparation method and application of the film.
In order to achieve the above object, the technical scheme of the present invention is as follows:
ion implantation-based p-type polycrystalline beta-Ga 2 O 3 The preparation method of the film comprises the following steps:
step 1) adopting an ion implantation process to implant oxygen ions into the GaN wafer, wherein the implantation energy is 200-300 kev, and the implantation dosage is 1 multiplied by 10 19 ～1.5×10 19 ions/cm 2 Forming an amorphous or polycrystalline compound film layer of gallium oxynitride in the implantation depth with an implantation current of 25-35 mu A, wherein O: the atomic proportion of Ga is more than or equal to 1.5;
step 2) at N 2 Thermal annealing is carried out under the atmosphere, the temperature is 850-950 ℃, and the amorphous or polycrystalline compound film layer of the gallium oxynitride with at least partial depth is converted into N-doped p-type polycrystalline beta-Ga 2 O 3 A film.
Alternatively, the oxygen ion is a positive monovalent O + Ion or orthodivalent O 2+ Ions.
Optionally, the GaN wafer is an undoped (0001) plane single crystal GaN wafer, and the thickness of the GaN layer is 3-4 μm.
Optionally, the implantation depth is 880 nm-1.35 μm.
Optionally, the implantation time of the ion implantation is 25-35 min, and the implantation temperature is room temperature.
Optionally, the thermal annealing time is 30-40 min, and the formed p-type polycrystal beta-Ga 2 O 3 The thickness of the film is 920 nm-1.39 mu m.
Optionally, the method further comprises: step 3) p-type polycrystalline beta-Ga formed 2 O 3 And carrying out flattening treatment on the surface of the film, wherein the flattening treatment comprises dry etching by adopting an inductively coupled plasma etching process.
P-type polycrystalline beta-Ga prepared by the preparation method 2 O 3 A film having a hole carrier concentration of 10 18 cm -3 On the order of magnitude of (2).
An ultraviolet light detector comprises the p-type polycrystal beta-Ga 2 O 3 Thin film and p-type polycrystalline beta-Ga 2 O 3 Interdigital structural gold on film surfaceBelongs to an electrode.
The preparation method of the ultraviolet light detector comprises the following steps:
step A: preparing a semiconductor substrate for forming an ultraviolet light detector by adopting a GaN wafer through the preparation method;
and (B) step (B): p-type polycrystalline beta-Ga on semiconductor substrate 2 O 3 Preparing an interdigital structure metal electrode on the surface of the film by sputtering metal Zn, and forming a metal electrode with an interdigital structure on N 2 Carrying out rapid thermal annealing in atmosphere at the annealing temperature of 350-400 ℃ for 50-80 seconds to form the p-type beta-Ga-based alloy 2 O 3 Thin film metal-semiconductor-metal structured ultraviolet light detector.
The beneficial effects of the invention are as follows:
the invention injects positive monovalent O into the GaN wafer with high injection energy and ultra-large injection dosage + (or orthodivalent O) 2+ ) Ions such that O: the atomic ratio of Ga is greater than or equal to Ga 2 O 3 The ideal atomic ratio of oxygen to gallium is 1.5. Within the ion implantation depth, amorphous or polycrystalline compounds of gallium oxynitride Ga-O-N are formed. Amorphous or polycrystalline gallium oxynitride Ga-O-N compounds are then efficiently converted to N-doped polycrystalline beta-Ga by high temperature annealing 2 O 3 Activating beta-Ga 2 O 3 And repairing the defects caused by ion implantation. P-type beta-Ga prepared 2 O 3 The film has better p-type electrical property, and the hole carrier concentration reaches 10 18 cm -3 The order of magnitude of (c) improves the performance of the application device.
Drawings
FIG. 1 is a process flow diagram of an embodiment;
FIG. 2 is an X-ray diffraction (XRD) pattern of example 1;
FIG. 3 is a schematic view of the semiconductor crystal structure+top surface Hall Zn electrode obtained in example 1;
FIG. 4 shows p-type beta-Ga of example 1 2 O 3 Ohmic I-V characteristic diagram of Zn electrode of the film;
FIG. 5 shows p-type beta-Ga of example 1 2 O 3 Film vacuum variable-temperature Hall test, wherein the Hall coefficient changes along with the test temperatureA figure;
FIG. 6 shows p-type beta-Ga of example 1 2 O 3 Film vacuum variable temperature Hall test, wherein the concentration of hole carriers of the Hall is a graph along with the temperature change of the test;
FIG. 7 shows p-type beta-Ga of example 1 2 O 3 Film vacuum variable temperature Hall test, hole mobility with test temperature change diagram;
FIG. 8 shows p-type beta-Ga of example 1 2 O 3 Film vacuum variable temperature Hall test, resistivity with test temperature change diagram;
FIG. 9 is a schematic diagram of the semiconductor crystal structure + top electrode of the MSM ultraviolet light detector of example 3;
FIG. 10 is an I-t characteristic curve of the ultraviolet light detector of example 3.
Detailed Description
The invention is further explained below with reference to the drawings and specific embodiments. The drawings of the present invention are merely schematic to facilitate understanding of the present invention, and specific proportions thereof may be adjusted according to design requirements. The definition of the context of the relative elements and the front/back of the figures described herein should be understood by those skilled in the art to refer to the relative positions of the elements and thus all the elements may be reversed to represent the same elements, which are all within the scope of the present disclosure.
Example 1
Refer to the preparation process flow diagram of fig. 1. The GaN used in the examples was purchased from undoped (0001) -plane single crystal GaN wafer prepared by MOCVD method on sapphire substrate of Shanghai optical precision mechanical institute of China academy of sciences, the GaN layer thickness was 4 μm, n-type, and the room temperature Hall electron doping concentration was 8.87×10 16 cm -3 . Before ion implantation is started, the GaN wafer is first cleaned in the order of "acetone (ultrasonic cleaning for 15 minutes)" → "ethanol (ultrasonic cleaning for 15 minutes)" → "deionized water (ultrasonic cleaning for 15 minutes)", to remove surface impurities and oxides.
Step one ion implantation
Table 1 example 1 ion implantation parameter table
Using ion implantation techniques, positive monovalent O is implanted into GaN wafers at high implantation energies and ultra-high implantation doses, with reference to the parameters of Table 1 + Ions. Based on SRIM-2016 simulation, the implantation depth is obtained to be 880nm, O + Ion peak concentration of 2.12X10 23 cm -3 O within depth range + The average concentration of ions was 1.05X10 23 cm -3 。
The bonding mode of Ga-N of GaN is that Ga and N form three covalent bonds and one coordination bond, and the bond energy is high and is 876.9kJ/mol. The ion implantation adopts high implantation energy, the implantation oxygen ion has high energy, and under the impact of the ion, the effective bond breaking of Ga-N bonds is facilitated. And more importantly: the ion implantation adopts the ultra-large implantation dosage of 1.5 multiplied by 10 19 (ions/cm 2 ) So that within 880nm implantation depth, average O + Up to a doping concentration of 1.05X10) 23 cm -3 So that O: the atomic ratio of Ga is greater than or equal to Ga 2 O 3 The ideal atomic ratio of oxygen to gallium is 1.5. Within the depth of ion implantation, amorphous or polycrystalline compounds of gallium oxynitride Ga-O-N are formed, whose XRD characteristic pattern is shown in curve (1) of FIG. 2.
Step two annealing
At N 2 Thermal annealing was performed under an atmosphere for 30 minutes at 900 ℃. Under the action of high temperature, partial N ions escape sample wafer and simultaneously, amorphous or polycrystalline compound of gallium oxynitride Ga-O-N is converted into N-doped p-type polycrystalline beta-Ga 2 O 3 The XRD pattern is shown in curve (2) of FIG. 2. Formed p-type polycrystalline beta-Ga 2 O 3 The thickness of the film was about 920nm. Annealing also can partially reduce doped N p-type polycrystalline beta-Ga 2 O 3 Is a defect in (a).
Step three film surface planarization
P-type polycrystalline beta-Ga formed by ICP (inductively coupled plasma etching) dry etching 2 O 3 Film Surface (SF) 6 The flow ratio of Ar to Ar is 3:1), so that the surface of the film is flatAnd (5) melting.
The obtained semiconductor structure comprises an undoped GaN layer 1, an O-doped GaN layer 2 and an N-doped p-type polycrystalline beta-Ga from bottom to top 2 O 3 And a film 3. Using divalent metal Zn (zinc) as ohmic contact electrode 4, using magnetron sputtering process, in beta-Ga 2 O 3 The surface of the film is sputtered with a metal electrode, and the thickness of the electrode is 150nm. Then carrying out Rapid Thermal Annealing (RTA) on the metal electrode for 60 seconds, wherein the atmosphere is N 2 The temperature of the gas is 350-400 ℃. The example uses a RTA temperature of 360 ℃. After the ohmic contact is completed, the obtained atomic structure schematic diagram is shown in fig. 3, and the electrode is subjected to an I-V characteristic test, and as a result, as shown in fig. 4, the ohmic contact electrical characteristic verified by good I-V characteristic linearity is good.
And (3) testing the variable-temperature Hall in a vacuum environment, wherein the temperature range of the variable-temperature Hall is 150K-700K. The hall coefficients of the variable temperature hall test are shown in fig. 5, and positive hall coefficients prove that p-type beta-Ga 2 O 3 The film preparation was successful. Hole carrier concentrations are shown in fig. 6; hole mobility is shown in fig. 7; the resistivity is shown in fig. 8.
As can be seen from the figure, p-type polycrystalline beta-Ga is obtained 2 O 3 Film, hall hole carrier concentration at room temperature 300K is 4.54839 ×10 18 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the Hole resistivity was 0.036844 (Ω·cm); hole mobility of 21.7971 (cm) 2 /V·s)。
Example 2
Example 2 uses the same GaN wafer and wafer cleaning is performed prior to ion implantation.
Step one ion implantation
Table 2 example 2 ion implantation parameters table
Reference is made to the parameters of Table 2 using ion implantation techniques toHigh implantation energy and ultra-large implantation dose, and positive monovalent O is implanted into the GaN wafer + Ions. Based on SRIM-2016 simulation, the implantation depth is obtained to be 880nm, O + Ion peak concentration of 1.82×10 23 cm -3 O within depth range + The average concentration of ions was 9.01X10 22 cm -3 。
Step two annealing
At N 2 Thermal annealing was performed under an atmosphere for 30 minutes at 900 ℃. Under the action of high temperature, partial N ions escape sample wafer and simultaneously, amorphous or polycrystalline compound of gallium oxynitride Ga-O-N is converted into N-doped p-type polycrystalline beta-Ga 2 O 3 The XRD pattern is shown in curve (2) of FIG. 1. Formed p-type polycrystalline beta-Ga 2 O 3 The thickness of the film was about 920nm.
Step three film surface planarization
P-type polycrystalline beta-Ga formed by ICP (inductively coupled plasma etching) dry etching 2 O 3 Film Surface (SF) 6 The flow ratio to Ar is 3:1), and the surface of the film is flattened.
The obtained semiconductor structure comprises an undoped GaN layer 1, an O-doped GaN layer 2 and an N-doped p-type polycrystalline beta-Ga from bottom to top 2 O 3 And a film 3. Using divalent metal Zn (zinc) as ohmic contact electrode 4, using magnetron sputtering process, in beta-Ga 2 O 3 The surface of the film is sputtered with a metal electrode, and the thickness of the electrode is 150nm. Then carrying out Rapid Thermal Annealing (RTA) on the metal electrode for 60 seconds, wherein the atmosphere is N 2 The temperature of the gas was 360 ℃.
And (3) testing the variable-temperature Hall in a vacuum environment, wherein the temperature range of the variable-temperature Hall is 150K-700K. Positive hall coefficient of temperature change hall test proves that p-type beta-Ga 2 O 3 The film preparation was successful. The p-type polycrystal beta-Ga 2 O 3 Film, hall hole carrier concentration at room temperature 300K is 2.91×10 18 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the Hole resistivity was 0.042417 (Ω·cm); hole mobility of 23.0721 (cm) 2 /V·s)。
Example 3
In this example, zinc Zn was used for sputteringAn interdigital structure metal electrode of an ultraviolet photoelectric detector is provided, wherein the length of the interdigital structure metal electrode is 900 mu m, the width of the interdigital structure metal electrode is 200 mu m, the up-down distance of the interdigital structure metal electrode is 200 mu m, the left-right gap is 100 mu m, and the longitudinal thickness of the interdigital electrode is 150nm. An interdigital metal electrode 5 was formed on the p-type beta-Ga obtained in example 1 2 O 3 The surface of the film 3 is contacted with ohmic contact, and the ultraviolet light detector with a metal-semiconductor-metal (MSM) structure is prepared, as shown in fig. 9.
At a power density of 1.35mW/cm under a 10V bias 2 The time response (I-t) characteristics of the 254nm UV light irradiation are shown in FIG. 10. Wherein FIG. 10 (a) is a graph showing the measured logarithmic scale multicycle I-t characteristic curve, the stabilized photocurrent being 1.7X10 under 254nm ultraviolet irradiation -3 A. Fig. 10 (b) shows that rise and decay times are extracted from the photocurrent response. Under 254nm illumination, the photodetector showed a faster response speed, a rise time of 34ms and a decay time of 32ms.
The above examples are only for further illustration of one ion implantation-based p-type polycrystalline beta-Ga of the present invention 2 O 3 The preparation method and application of the film are not limited to the embodiment, and any simple modification, equivalent variation and modification of the above embodiment according to the technical substance of the invention fall within the protection scope of the technical proposal of the invention.

Claims (10)

1. Ion implantation-based p-type polycrystalline beta-Ga 2 O 3 The preparation method of the film is characterized by comprising the following steps:
step 1) adopting an ion implantation process to implant oxygen ions into the GaN wafer, wherein the implantation energy is 200-300 kev, and the implantation dosage is 1 multiplied by 10 19 ～1.5×10 19 ions/cm 2 Forming an amorphous or polycrystalline compound film layer of gallium oxynitride in the implantation depth with an implantation current of 25-35 mu A, wherein O: the atomic proportion of Ga is more than or equal to 1.5;
step 2) at N 2 Thermal annealing is carried out under the atmosphere, the temperature is 850-950 ℃, and the amorphous or polycrystalline compound film layer of the gallium oxynitride with at least partial depth is converted into N-doped p-type polycrystalline beta-Ga 2 O 3 A film.
2. Ion implantation-based p-type polycrystalline beta-Ga of claim 1 2 O 3 The preparation method of the film is characterized in that: the oxygen ion is positive monovalent O + Ion or orthodivalent O 2+ Ions.
3. Ion implantation-based p-type polycrystalline beta-Ga of claim 1 2 O 3 The preparation method of the film is characterized in that: the GaN wafer is a single crystal GaN wafer with an undoped (0001) plane, and the thickness of the GaN layer is 3-4 mu m.
4. Ion implantation-based p-type polycrystalline beta-Ga of claim 1 2 O 3 The preparation method of the film is characterized in that: the implantation depth is 880nm to 1.35 mu m.
5. Ion implantation-based p-type polycrystalline beta-Ga of claim 1 2 O 3 The preparation method of the film is characterized in that: the implantation time of the ion implantation is 25-35 min, and the implantation temperature is room temperature.
6. Ion implantation-based p-type polycrystalline beta-Ga of claim 1 2 O 3 The preparation method of the film is characterized in that: the thermal annealing time is 30-40 min, and the formed p-type polycrystal beta-Ga 2 O 3 The thickness of the film is 920 nm-1.39 mu m.
7. Ion implantation-based p-type polycrystalline beta-Ga of claim 1 2 O 3 The preparation method of the film is characterized by further comprising the following steps:
step 3) p-type polycrystalline beta-Ga formed 2 O 3 And carrying out flattening treatment on the surface of the film, wherein the flattening treatment comprises dry etching by adopting an inductively coupled plasma etching process.
8. Root of Chinese characterP-type polycrystalline beta-Ga prepared by the preparation method according to any one of claims 1 to 7 2 O 3 The film is characterized in that: the hole carrier concentration of the film is 10 18 cm -3 On the order of magnitude of (2).
9. An ultraviolet light detector, characterized in that: comprising the p-type polycrystalline beta-Ga of claim 8 2 O 3 Thin film and p-type polycrystalline beta-Ga 2 O 3 And an interdigital structure metal electrode on the surface of the film.
10. The preparation method of the ultraviolet light detector is characterized by comprising the following steps of:
step A: preparing a semiconductor substrate for forming an ultraviolet light detector by the preparation method of any one of claims 1 to 7 by using a GaN wafer;
and (B) step (B): p-type polycrystalline beta-Ga on semiconductor substrate 2 O 3 Preparing an interdigital structure metal electrode on the surface of the film by sputtering metal Zn, and forming a metal electrode with an interdigital structure on N 2 Carrying out rapid thermal annealing in atmosphere at the annealing temperature of 350-400 ℃ for 50-80 seconds to form the p-type beta-Ga-based alloy 2 O 3 Thin film metal-semiconductor-metal structured ultraviolet light detector.
CN202310949190.0A 2023-07-31 2023-07-31 Ion implantation-based p-type polycrystalline beta-Ga 2 O 3 Preparation method and application of film Pending CN116741625A (en)

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