CN108962732B - ZnMgO film and preparation method thereof - Google Patents

ZnMgO film and preparation method thereof Download PDF

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CN108962732B
CN108962732B CN201810764417.3A CN201810764417A CN108962732B CN 108962732 B CN108962732 B CN 108962732B CN 201810764417 A CN201810764417 A CN 201810764417A CN 108962732 B CN108962732 B CN 108962732B
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znmgo film
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陈星�
刘可为
李炳辉
张振中
申德振
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Abstract

The invention provides a preparation method of a ZnMgO film, which comprises the following steps: an organic zinc compound is used as a zinc source, an organic magnesium compound is used as a magnesium source, and a ZnMgO film is grown on a substrate in a metal organic compound chemical vapor deposition device which is introduced with oxygen. Compared with the prior art, the method for preparing the ZnMgO film by using the metal organic compound chemical vapor deposition method has the advantages that the airflow is parallel to the substrate, the growth temperature is low, the prepared ZnMgO film has the characteristics of high crystallization quality, no phase separation, steep absorption edge cutting and the like, the preparation method has potential application prospect in the preparation method of photoelectric devices, the preparation process is simple, and the reaction process is easy to control.

Description

ZnMgO film and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a ZnMgO film and a preparation method thereof.
Background
The ultraviolet detection technology can be used for military communication, missile tail flame detection, fire early warning, environmental monitoring, biological effect and the like, and can be widely applied to military affairs and civil use. Ultraviolet rays with wavelengths below 280nm in solar radiation are almost absent on the earth's surface due to the strong absorption of the atmosphere, and this ultraviolet band is figuratively called the solar blind band. The solar blind ultraviolet detector working in the wave band is not interfered by solar radiation, has higher sensitivity and has outstanding advantages in the aspect of weak signal detection.
Currently, commercially available ultraviolet detectors mainly include silicon detectors, photomultiplier tubes, and semiconductor detectors. The silicon-based ultraviolet phototube needs an additional optical filter, the photomultiplier needs to work under high voltage, and the photomultiplier has the advantages of heavy volume, low efficiency, easy damage and higher cost, and has certain limitation on practical application. Compared with silicon detectors and photomultiplier tubes, semiconductor materials are attracting much attention because of their advantages of portability, low cost, high responsivity, etc.
The most studied semiconductor materials at present mainly comprise AlGaN alloy of III-V group and ZnMgO alloy of II-VI group. The currently reported GaN can broaden the energy band to the solar blind area by doping aluminum, and is made into detectors with structures such as MSM, p-n and the like. However, the growth temperature of AlGaN is high, and the alloy crystal quality of the high aluminum component is poor. ZnMgO has the advantages of wide band gap adjusting range (from 3.37eV to 7.8eV), strong radiation resistance, high electron saturation drift velocity, matched single crystal substrates (ZnO and MgO), easy synthesis, no toxicity, no harm, rich resources, environmental friendliness and the like, and is one of candidate materials for preparing wide-bandgap ultraviolet detectors, particularly solar-blind ultraviolet detectors.
However, when growing the ZnMgO material, due to the particularity of the material, phase separation is often encountered, or the components are widened, so that the absorption cut-off edge is smoothed, which is very disadvantageous for the material application and the preparation of an ultraviolet detection device.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a ZnMgO film having a single cubic phase and a method for preparing the same.
The invention provides a preparation method of a ZnMgO film, which comprises the following steps:
an organic zinc compound is used as a zinc source, an organic magnesium compound is used as a magnesium source, and a ZnMgO film is grown on a substrate in a metal organic compound chemical vapor deposition device which is introduced with oxygen.
Preferably, the organic zinc compound is diethyl zinc and/or dimethyl zinc; the organic magnesium compound is dimethyl cyclopentadienyl magnesium and/or cyclopentadienyl magnesium.
Preferably, the organic zinc compound takes a first protective gas as a carrier gas; the flow rate of the first protective gas is 10-20 ml/min; the organomagnesium compound takes a second protective gas as a carrier; the flow rate of the second protective gas is 10-100 ml/min.
Preferably, the growth temperature is 350-550 ℃; the growth time is 0.5-5 h.
Preferably, the vacuum degree of the growth is 1X 104～3×104Pa。
Preferably, the flow rate of the oxygen is 150-1850 ml/min.
Preferably, after the growth is finished, cooling to room temperature to obtain a ZnMgO film; the cooling rate is 1-15 ℃/min.
Preferably, the substrate is a sapphire substrate, a silicon wafer with a surface covered with a rear silicon dioxide layer, or quartz glass.
The invention also provides a ZnMgO film, wherein the crystal structure of the ZnMgO film is a cubic phase; the absorption cutoff edge of the ZnMgO film is 220-240 nm.
Preferably, the thickness of the ZnMgO film is 100-600 nm.
The invention provides a preparation method of a ZnMgO film, which comprises the following steps: an organic zinc compound is used as a zinc source, an organic magnesium compound is used as a magnesium source, and a ZnMgO film is grown on a substrate in a metal organic compound chemical vapor deposition device which is introduced with oxygen. Compared with the prior art, the method for preparing the ZnMgO film by using the metal organic compound chemical vapor deposition method has the advantages that the airflow is parallel to the substrate, the growth temperature is low, the prepared ZnMgO film has the characteristics of high crystallization quality, no phase separation, steep absorption edge cutting and the like, the preparation method has potential application prospect in the preparation method of photoelectric devices, the preparation process is simple, and the reaction process is easy to control.
Drawings
FIG. 1 is a scanning electron micrograph of a ZnMgO thin film obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of a ZnMgO thin film obtained in example 1 of the present invention;
FIG. 3 is a UV-VIS absorption spectrum of the ZnMgO film obtained in example 1 of the present invention;
FIG. 4 is an ultraviolet-visible absorption spectrum of the ZnMgO thin film layer obtained in examples 7 to 8 of the present invention;
FIG. 5 is a spectral response spectrum of the ZnMgO ultraviolet detector obtained in embodiments 7 to 8 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a ZnMgO film, wherein the crystal structure of the ZnMgO film is a cubic phase; the absorption cut-off edge of the ZnMgO film is 220-240 nm, preferably is positioned near 230nm, and is very steep; the thickness of the ZnMgO film is preferably 100-600 nm, more preferably 200-500 nm, still more preferably 300-500 nm, and most preferably 400 nm; the mol ratio of Zn to Mg in the ZnMgO film is preferably (1-4): (9-6), more preferably (1.5-4): (8.5-5), and more preferably (1.8-4): (8.2-5), most preferably (1.8-3.9): (8.2-6.1); in some embodiments provided herein, the molar ratio of Zn to Mg is preferably 3: 7; in some embodiments provided herein, the Zn to Mg molar ratio is preferably 1.8: 8.2; in other embodiments provided herein, the Zn to Mg molar ratio is preferably 3.9: 6.1. .
The invention also provides a preparation method of the ZnMgO film, which comprises the following steps: an organic zinc compound is used as a zinc source, an organic magnesium compound is used as a magnesium source, and a ZnMgO film is grown on a substrate in a metal organic compound chemical vapor deposition device which is introduced with oxygen.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The organic zinc compound is an organic zinc compound well known to those skilled in the art, and is not particularly limited, and in the present invention, dialkyl zinc is preferred, dialkyl zinc with alkyl carbon number of 1-5 is more preferred, and diethyl zinc and/or dimethyl zinc are further preferred; the organomagnesium compound is not particularly limited as long as it is an organomagnesium compound well known to those skilled in the art, and in the present invention, a magnesium metallocene and/or a dialkylmagnesium metallocene is preferable; the number of carbon atoms of alkyl in the dialkyl magnesium dicyclopentadienyl is preferably 1-5, more preferably 1-3, and still more preferably 1-2.
The invention takes an organic zinc compound as a zinc source, and takes a first protective gas as a carrier gas; the first protective gas is a protective gas known to those skilled in the art, and is not particularly limited, and in the present invention, nitrogen is preferable, and high-purity nitrogen is more preferable; the flow rate of the first protective gas is preferably 10-20 ml/min, more preferably 12-20 ml/min, still more preferably 14-18 ml/min, and most preferably 16 ml/min.
The invention takes an organic magnesium compound as a magnesium source, and takes a second protective gas as a carrier; the second protective gas is a protective gas known to those skilled in the art, and is not particularly limited, and in the present invention, nitrogen is preferred, and high-purity nitrogen is more preferred; the flow rate of the second protective gas is preferably 10-100 ml/min, more preferably 20-100 ml/min, and further preferably 30-80 ml/min; in some embodiments provided herein, the flow rate of the second shielding gas is preferably 30 ml/min; in some embodiments provided herein, the flow rate of the second shielding gas is preferably 50 ml/min; in other embodiments provided herein, the flow rate of the second shielding gas is preferably 80 ml/min.
The molar concentration ratio of zinc to magnesium in the ZnMgO film can be adjusted using different carrier gas ratios.
Growing a ZnMgO film on a substrate in a metal organic compound chemical vapor deposition device which is introduced with oxygen; the flow rate of the oxygen is preferably 150-1850 ml/min, more preferably 300-1500 ml/min, still more preferably 400-1200 ml/min, still more preferably 400-1000 ml/min, still more preferably 400-800 ml/min, still more preferably 400-600 ml/min, and most preferably 550 ml/min; the substrate is a substrate known to those skilled in the art, and is not particularly limited, and in the present invention, a sapphire substrate, a silicon wafer with a surface covered with a silicon dioxide layer, or quartz glass is preferred; the substrate is preferably used for growing a ZnMgO film after being cleaned and dried; the method of cleaning is well known to those skilled in the artThe method is not particularly limited, and in the present invention, it is preferable to wash with trichloroethylene, acetone, and ethanol in this order; the drying is preferably carried out by drying with dry nitrogen; the growth temperature is preferably 350-550 ℃, more preferably 400-550 ℃, further preferably 450-550 ℃, and most preferably 500-550 ℃; the growth time is preferably 0.5-5 h, more preferably 1-4 h, still more preferably 1-3 h, and most preferably 2 h; the degree of vacuum for the growth is preferably 1X 104～3×104Pa, more preferably 1.5X 104～2.5×104Pa, more preferably 2X 104Pa。
After the growth is finished, closing the organic source, and preferably cooling to room temperature to obtain a ZnMgO film; the cooling rate is preferably 1-15 ℃/min, more preferably 2-12 ℃/min, still more preferably 2-10 ℃/min, still more preferably 4-8 ℃/min, and most preferably 5-6 ℃/min.
The method prepares the ZnMgO film by using the metal organic compound chemical vapor deposition method, the airflow of the ZnMgO film is parallel to the substrate, and the growth temperature is lower, so that the prepared ZnMgO film has the characteristics of high crystalline quality, no phase separation, steep absorption cut edge and the like, has potential application prospect in the preparation method of photoelectric devices, and has simple preparation process and easily controlled reaction process.
In order to further illustrate the present invention, the following describes a ZnMgO film and a method for preparing the same in detail with reference to examples.
The reagents used in the following examples are all commercially available; in the examples, the substrate used had a thickness of 0.45 to 0.55mm, a 2-inch-sized wafer, and a square block of about 5 to 10mm by 5 to 10mm after cutting.
Example 1
1.1 the sapphire substrate was cleaned with trichloroethylene, acetone, ethanol, respectively, and then blown dry with dry nitrogen.
1.2 placing the sapphire substrate obtained in the step 1.1 into MOCVD growth equipment, adjusting the growth temperature to 550 ℃ and the vacuum degree of a growth chamber to be 2 multiplied by 104Pa, diethyl zinc as zinc source, dimethyl cyclopentadienyl magnesium as magnesium source, and different molar concentration ratios of zinc and magnesiumThe proportion of gas and carrier gas is adjusted, the flow rate of the introduced oxygen is 550mL/min, the flow rate of the carrier gas of the diethyl zinc pipeline is 16mL/min, and the flow rate of the carrier gas of the dimethyl magnesium metallocene pipeline is 50 mL/min.
And (3) growing for 2 hours, closing the organic source, reducing the temperature at the speed of 5 ℃/min, finally reducing the temperature to room temperature, and taking out the substrate to obtain the ZnMgO film, wherein the molar ratio of Zn to Mg in the film is 3: 7.
The ZnMgO thin film obtained in example 1 was analyzed by a Scanning Electron Microscope (SEM) to obtain a SEM photograph, and as shown in FIG. 1, the ZnMgO thin film obtained in example 1 was uniform in thickness, about 400nm, as seen in FIG. 1.
The ZnMgO film obtained in example 1 was analyzed by X-ray to obtain an X-ray diffraction (XRD) spectrum, as shown in fig. 2. As can be seen from FIG. 2, the obtained film has a cubic phase structure, no other crystals exist, and the absorption peak of XRD is sharp, which indicates that the crystal quality is high.
The ultraviolet-visible light absorption spectrum of the ZnMgO film obtained in example 1 was detected to obtain a UV-Vis spectrum thereof, as shown in fig. 3. It can be seen from fig. 3 that the absorption cut-off is quite steep, with the cut-off lying near 230 nm.
Example 2
2.1 the sapphire substrate was cleaned with trichloroethylene, acetone, ethanol, respectively, and then blown dry with dry nitrogen.
2.2 placing the sapphire substrate obtained in the step 2.1 into MOCVD growth equipment, adjusting the growth temperature to 550 ℃ and the vacuum degree of a growth chamber to be 2 multiplied by 104Pa, using diethyl zinc as a zinc source, using dimethyl magnesium as a magnesium source, adjusting the molar concentration ratio of zinc and magnesium by using different high-purity nitrogen carrier gas ratios, and leading in oxygen at a flow rate of 550mL/min, the carrier gas flow rate of a diethyl zinc pipeline at 16mL/min, and the carrier gas flow rate of a dimethyl magnesium pipeline at 80 mL/min.
2.3, growing for 2 hours, closing the organic source, reducing the temperature at the speed of 5 ℃/min, finally reducing the temperature to the room temperature, taking out the substrate, and obtaining the ZnMgO film, wherein the molar ratio of Zn to Mg in the film is 1.8: 8.2.
The ultraviolet-visible light absorption spectrum of the ZnMgO film obtained in example 2 was measured, and the absorption edge thereof was located at about 220 nm.
Example 3
3.1 cleaning the sapphire substrate by using trichloroethylene, acetone and ethanol respectively, and then drying by using dry nitrogen.
3.2 placing the sapphire substrate obtained in the step 3.1 into MOCVD growth equipment, adjusting the growth temperature to 550 ℃ and the vacuum degree of a growth chamber to be 2 multiplied by 104Pa, using diethyl zinc as a zinc source, using dimethyl magnesium as a magnesium source, adjusting the molar concentration ratio of zinc and magnesium by using different high-purity nitrogen carrier gas ratios, and leading in oxygen at a flow rate of 550mL/min, the carrier gas flow rate of a diethyl zinc pipeline at 16mL/min, and the carrier gas flow rate of a dimethyl magnesium pipeline at 30 mL/min.
3.3, growing for 2 hours, closing the organic source, reducing the temperature at the speed of 5 ℃/min, finally reducing the temperature to the room temperature, taking out the substrate, and obtaining the ZnMgO film, wherein the molar ratio of Zn to Mg in the film is 3.9: 6.1.
By detecting the ultraviolet-visible light absorption spectrum of the ZnMgO film obtained in example 3, a ZnMgO film having an absorption edge of about 240nm was obtained.
Example 4
4.1 the sapphire substrate was cleaned with trichloroethylene, acetone, ethanol, respectively, and then blown dry with dry nitrogen.
4.2 placing the sapphire substrate obtained in the step 4.1 into MOCVD growth equipment, adjusting the growth temperature to 550 ℃ and the vacuum degree of a growth chamber to be 2 multiplied by 104Pa, using diethyl zinc as a zinc source, using dicyclopentadienyl magnesium as a magnesium source, adjusting the molar concentration ratio of zinc and magnesium by using different high-purity nitrogen carrier gas ratios, and leading in oxygen at a flow rate of 550mL/min, the carrier gas flow rate of a diethyl zinc pipeline at 16mL/min, and the carrier gas flow rate of a dicyclopentadienyl magnesium pipeline at 50 mL/min.
4.3 growing for 2 hours, closing the organic source, reducing the temperature at the speed of 5 ℃/min, finally reducing the temperature to the room temperature, and taking out the substrate to obtain the ZnMgO film.
The ZnMgO thin film obtained in example 4 was analyzed by a Scanning Electron Microscope (SEM) to obtain a SEM photograph, and as shown in FIG. 1, it can be seen from FIG. 1 that the ZnMgO thin film obtained in example 4 has a uniform thickness of about 400 nm.
The ultraviolet-visible absorption spectrum of the ZnMgO film obtained in example 4 was measured, and the absorption edge thereof was located at about 230 nm.
Example 5
5.1 the sapphire substrate was cleaned with trichloroethylene, acetone, ethanol, respectively, and then blown dry with dry nitrogen.
5.2 placing the sapphire substrate obtained in the step 5.1 into MOCVD growth equipment, adjusting the growth temperature to 550 ℃ and the vacuum degree of a growth chamber to be 2 multiplied by 104Pa, using dimethyl zinc as a zinc source, using dimethyl magnesium as a magnesium source, adjusting the molar concentration ratio of zinc and magnesium by using different high-purity nitrogen carrier gas ratios, and introducing oxygen at a flow rate of 550mL/min, dimethyl zinc at a flow rate of 16mL/min, and dimethyl magnesium at a flow rate of 50 mL/min.
5.3 growing for 2 hours, closing the organic source, reducing the temperature at the speed of 5 ℃/min, finally reducing the temperature to the room temperature, and taking out the substrate to obtain the ZnMgO film.
The ultraviolet-visible absorption spectrum of the ZnMgO film obtained in example 5 was examined, and it was possible to obtain a ZnMgO film having an absorption edge of about 230 nm.
Example 6
6.1 the sapphire substrate was cleaned with trichloroethylene, acetone, ethanol, respectively, and then blown dry with dry nitrogen.
6.2 placing the sapphire substrate obtained in the step 6.1 into MOCVD growth equipment, adjusting the growth temperature to 550 ℃ and the vacuum degree of a growth chamber to be 2 multiplied by 104Pa, using diethyl zinc as a zinc source, using dimethyl magnesium as a magnesium source, adjusting the molar concentration ratio of zinc and magnesium by using different high-purity nitrogen carrier gas ratios, and leading in oxygen at a flow rate of 550mL/min, the carrier gas flow rate of a diethyl zinc pipeline at 16mL/min, and the carrier gas flow rate of a dimethyl magnesium pipeline at 50 mL/min.
6.3 growing for 1 hour, closing the organic source, reducing the temperature at the speed of 5 ℃/min, finally reducing the temperature to the room temperature, and taking out the substrate to obtain the ZnMgO film.
The ultraviolet-visible absorption spectrum of the ZnMgO film obtained in example 6 was measured, and the absorption edge thereof was located at about 230 nm. The thickness is about 200 nm.
Example 7
7.1 the sapphire substrate was cleaned with trichloroethylene, acetone, ethanol, respectively, and then blown dry with dry nitrogen.
7.2 placing the sapphire substrate in the 7.1 into MOCVD growth equipment, adjusting the growth temperature to 450 ℃, and adjusting the vacuum degree of a growth chamber to be 1 multiplied by 104Pa, using diethyl zinc as a zinc source, using dimethyl magnesium as a magnesium source, adjusting the molar concentration ratio of zinc and magnesium by using different high-purity nitrogen carrier gas ratios, and leading oxygen flow rate to be 150mL/min, the carrier gas flow rate of a diethyl zinc pipeline to be 15mL/min, and the carrier gas flow rate of a dimethyl magnesium pipeline to be 50 mL/min.
7.3 growing for 2 hours, closing the organic source, reducing the temperature at the cooling rate of 5 ℃/min, finally reducing the temperature to the room temperature, and taking out the substrate to obtain the substrate with the ZnMgO film layer.
7.4 the sample obtained in 7.3 was placed in a vacuum coater at a pressure of 1X 10-3Under Pa, 50mg of Au particles were evaporated onto the sample surface using an evaporation current of 140A.
7.5, photoetching and wet etching the surface of the sample obtained In the step 7.4 to obtain a gold interdigital electrode, and pressing In particles on the interdigital electrode to obtain the ZnMgO ultraviolet detector with the MSM structure.
The ultraviolet-visible light absorption spectrum of the ZnMgO thin film layer obtained in example 7 was measured, and the spectrum thereof was as shown in fig. 4, from which it was seen that the light absorption cutoff edge of the ZnMgO thin film layer was located near 230 nm.
The photoresponse of the ZnMgO ultraviolet detector obtained in example 7 was detected, and the obtained photoresponse spectrum is shown in fig. 5, from which it can be seen that the photoresponse cut-off edge of the detector in example 7 is located near 350 nm.
Example 8
In order to examine the effect of the oxygen flow rate on the device fabrication, only the oxygen flow rate was changed, and the other conditions were the same as in example 7, to obtain a series of ultraviolet light detecting devices. The oxygen flow rates are 750mL/min, 1350mL/min and 1850mL/min respectively.
FIG. 4 is an ultraviolet-visible absorption spectrum of the ZnMgO thin film layer, and it can be seen from the graph that the light absorption cut-off edges of the ZnMgO thin film layer are not changed with the change of the oxygen flow rate and are all located near 230 nm.

Claims (2)

1. A preparation method of a ZnMgO film is characterized by comprising the following steps:
growing a ZnMgO film on a substrate in a metal organic compound chemical vapor deposition device with oxygen introduced by taking an organic zinc compound as a zinc source and an organic magnesium compound as a magnesium source;
the ZnMgO film comprises Zn and Mg in a molar ratio of (1-4): (9-6);
the organic zinc compound takes a first protective gas as a carrier gas; the flow rate of the first protective gas is 15-16 ml/min; the organomagnesium compound takes a second protective gas as a carrier; the flow rate of the second protective gas is 30-80 ml/min;
the growth temperature is 450-550 ℃; the growth time is 0.5-5 h;
the flow rate of the oxygen is 150-1850 ml/min;
after the growth is finished, cooling to room temperature to obtain a ZnMgO film; the cooling rate is 5 ℃/min;
the organic zinc compound is diethyl zinc and/or dimethyl zinc; the organic magnesium compound is dimethyl cyclopentadienyl magnesium and/or cyclopentadienyl magnesium;
the vacuum degree of the growth is 1 × 104～2×104Pa；
The crystal structure of the ZnMgO film is a cubic phase; the absorption cut-off edge of the ZnMgO film is 220-240 nm;
the thickness of the ZnMgO film is 100-600 nm;
fixing other parameters, and only adjusting the oxygen flow to obtain the ZnMgO film layer with the same light absorption cut-off edge.
2. The method according to claim 1, wherein the substrate is a sapphire substrate, a silicon wafer with a surface covered with a rear silicon dioxide layer, or quartz glass.
CN201810764417.3A 2018-07-12 2018-07-12 ZnMgO film and preparation method thereof Active CN108962732B (en)

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