阅读说明：本技术 磷掺杂β-Ga2O3微米线的制备方法 (Phosphorus doped beta-Ga2O3Preparation method of micron line ) 是由 冯秋菊 高冲 解金珠 董增杰 孙景昌 梁硕 刘玮 于 2021-01-08 设计创作，主要内容包括：本发明公开一种磷掺杂β-Ga-2O-3微米线的制备方法,将纯度大于99.9%的氧化镓粉末、碳粉和P-2O-5粉末按质量比6:9:1～2配比混合制成反应源材料,将反应源材料放入刚玉舟内,再将刚玉舟放入化学气相沉积系统石英管的中心处,衬底位于反应源材料上方1～2cm处；通入氩气,氩气流量控制在300ml/min；当加热温度达到1100℃时通入氧气,氧气流量控制在300ml/min,生长时间为20～40分钟；关闭氧气,保持氩气流量,降温至室温,取出样品。从微米线样品底部剥离出单根的微米线,在其两端滴定银胶电极,即可制备单根磷掺杂β-Ga-2O-3微米线紫外探测器,比未掺杂β-Ga-2O-3微米线探测器具有更好的紫外探测性能。(The invention discloses phosphorus-doped beta-Ga 2 O 3 The preparation method of micron line comprises mixing gallium oxide powder with purity of more than 99.9%, carbon powder and P 2 O 5 Mixing the powder according to the mass ratio of 6:9: 1-2 to prepare a reaction source material, putting the reaction source material into a corundum boat, putting the corundum boat into the center of a quartz tube of a chemical vapor deposition system, and positioning a substrate 1-2 cm above the reaction source material; introducing argon, wherein the flow rate of the argon is controlled at 300 ml/min; when the heating temperature reaches 1100 ℃, introducing oxygen, controlling the flow of the oxygen at 300ml/min, and controlling the growth time to be 20-40 minutes; and closing the oxygen, keeping the flow of the argon, cooling to room temperature, and taking out the sample. Stripping a single microwire from the bottom of the microwire sample, titrating silver colloid electrodes at two ends of the microwire sample, and preparing the single phosphorus-doped beta-Ga 2 O 3 Micron ultraviolet detector, specific to undoped beta-Ga 2 O 3 The micron line detector has better ultraviolet detection performance.)

1. Phosphorus-doped beta-Ga₂O₃The preparation method of the micron line is characterized by comprising the following steps in sequence:

a. mixing gallium oxide powder with purity of more than 99.9%, carbon powder and P₂O₅Mixing the powder according to the mass ratio of 6:9: 1-2 to prepare a reaction source material, putting the reaction source material into a corundum boat, putting the corundum boat into the center of a quartz tube of a chemical vapor deposition system, and positioning a substrate 1-2 cm above the reaction source material;

b. introducing carrier gas argon, wherein the flow of the argon is controlled at 300 ml/min;

c. when the heating temperature reaches 1100 ℃, introducing oxygen, controlling the flow of the oxygen at 300ml/min, and controlling the growth time to be 20-40 minutes;

d. and closing the oxygen, keeping the flow of the argon, cooling to room temperature, and taking out the sample.

Technical Field

The invention belongs to the field of semiconductor devices, and particularly relates to phosphorus-doped beta-Ga₂O₃A preparation method of micron line.

Background

Monoclinic structure beta-Ga₂O₃Is a novel ultra-wide band gap (4.9 eV) semiconductor material, and has wide application prospect in the fields of new generation power electronic devices and photoelectric devices. In recent years, beta-Ga₂O₃The research of semiconductor materials mainly focuses on nano/micron materials and thin film materials, and compared with thin films and bulk materials, the nano/micron materials have superior performances such as high crystallization quality, quantum size effect, low-cost preparation and the like, and are widely concerned by scholars at home and abroad. The ozone layer has strong absorption effect on ultraviolet radiation of 200-280 nm, and beta-Ga₂O₃The ultra-wideband gap enables the absorption cut-off edge to be about 280nm, solar blind ultraviolet light can be well detected, the micro/nano structure has large surface volume ratio and good crystallization quality, and the sensitivity of the device can be remarkably increased, so that the beta-Ga material has beta-Ga₂O₃Micron lines have been applied to solar blind ultraviolet detectors. Currently single root of beta-Ga₂O₃The micron-line solar-blind ultraviolet detector is manufactured by using a single beta-Ga₂O₃Electrodes (conductive silver adhesive) are manufactured at two ends of the micron line and connected with a semiconductor parameter tester, and the result of ultraviolet detection is reflected by detecting the numerical value of the photocurrent of the device. However, beta-Ga is present₂O₃The microwires are mostly undoped beta-Ga₂O₃Nano/micro materials, up to now not seen for phosphorus doping of beta-Ga₂O₃Micron line and single phosphorus-doped beta-Ga capable of effectively improving ultraviolet detection performance₂O₃Related reports of micrometer ultraviolet detectors.

Disclosure of Invention

The present invention provides a phosphorus-doped beta-Ga for solving the above technical problems of the prior art₂O₃A preparation method of micron line.

The technical solution of the invention is as follows:phosphorus-doped beta-Ga₂O₃The preparation method of the micron line sequentially comprises the following steps:

a. mixing gallium oxide powder with purity of more than 99.9%, carbon powder and P₂O₅Mixing the powder according to the mass ratio of 6:9: 1-2 to prepare a reaction source material, putting the reaction source material into a corundum boat, putting the corundum boat into the center of a quartz tube of a chemical vapor deposition system, and positioning a substrate 1-2 cm above the reaction source material;

b. introducing carrier gas argon, wherein the flow of the argon is controlled at 300 ml/min;

c. when the heating temperature reaches 1100 ℃, introducing oxygen, controlling the flow of the oxygen at 300ml/min, and controlling the growth time to be 20-40 minutes;

d. and closing the oxygen, keeping the flow of the argon, cooling to room temperature, and taking out the sample.

The invention adopts a chemical vapor deposition method to prepare phosphorus-doped beta-Ga on a quartz boat and a substrate above a source material through oxidation and reduction reactions between the source material₂O₃Micron-scale wire, phosphorus-doped beta-Ga prepared therefrom₂O₃The diameter of the micron line is 30 to 50 μm, and the length is 0.6 to 1.0 cm. Stripping a single microwire from the bottom of the microwire sample, titrating silver colloid electrodes at two ends of the microwire sample, and preparing the single phosphorus-doped beta-Ga₂O₃Micrometer ultraviolet detector. Not only has simple manufacturing method and low cost, but also has better performance than the undoped beta-Ga₂O₃The micron line detector has better ultraviolet detection performance.

Drawings

FIG. 1 is a photograph of a physical camera of a sample prepared in example 1 of the present invention.

FIG. 2 is a single P-doped beta-Ga prepared in example 1 of the present invention₂O₃SEM photograph of microwire.

FIG. 3 is a single P-doped beta-Ga prepared in example 1 of the present invention₂O₃Energy dispersive spectrum of micron line.

Fig. 4 is a response time curve of a single phosphor-doped microwire detector fabricated in example 1 of the present invention under 254nm uv light.

FIG. 5 is an SEM photograph of a sample prepared in example 2 of the present invention.

Fig. 6 is a response time curve of a single phosphor-doped microwire detector fabricated in example 2 of the present invention under 254nm uv light.

FIG. 7 is a graph of response time of an undoped single microwire detector fabricated in accordance with comparative examples of the present invention under 254nm UV light.

Detailed Description

Examples 1 to 3 used conventional chemical vapor deposition equipment such as a tube furnace.

Example 1:

the phosphorus-doped beta-Ga of the invention₂O₃The preparation method of the micron line sequentially comprises the following steps:

a. mixing gallium oxide powder with purity of more than 99.9%, carbon powder and P₂O₅Mixing the powder according to the mass ratio of 6:9:1 to prepare a reaction source material, putting the reaction source material into a corundum boat, putting the corundum boat into the center of a quartz tube of a chemical vapor deposition system, and positioning a sapphire substrate 1.5cm above the reaction source material;

b. introducing carrier gas argon, wherein the flow of the argon is controlled at 300 ml/min;

c. when the heating temperature reaches 1100 ℃, oxygen is introduced, the oxygen flow is controlled at 300ml/min, and the growth time is 30 minutes;

d. and closing the oxygen, keeping the flow of the argon, cooling to room temperature, and taking out the sample.

FIG. 1 is phosphorus doped β -Ga prepared in example 1₂O₃The actual photo of the micrometer wire can be seen from fig. 1 that the micrometer wire has a large density and a length of 0.6 cm. FIG. 2 is a graph of example 1 showing a single phosphorus doped beta-Ga strip from the bottom of a sample substrate₂O₃SEM images of the microwires, fig. 2 shows that the diameter of a single microwire is about 40 μm. FIG. 3 Energy Dispersive Spectroscopy (EDS) of a single micron line prepared in example 1, it can be seen from FIG. 3 that for the phosphor-doped micron line, the presence of phosphorus elements was detected in addition to the Ga and O elements, with a phosphorus content of about 2 mole percent. FIG. 4 is a graph of response time of an UV detector made of a single microwire prepared in example 1 under 254nm UVAs can be seen from FIG. 4, the UV detector can be well modulated by UV light of 254nm, and shows excellent repeatability and stability during the test. The dark current value of the ultraviolet detector is about I_d=1.72nA, photocurrent was about I_l=2.0 μ a, light to dark current ratio of about (I)_l：I_d）1.16×10³。

Example 2:

the phosphorus-doped beta-Ga of the invention₂O₃The preparation method of the micron line sequentially comprises the following steps:

a. mixing gallium oxide powder with purity of more than 99.9%, carbon powder and P₂O₅Mixing the powder according to the mass ratio of 6:9:1.5 to prepare a reaction source material, putting the reaction source material into a corundum boat, putting the corundum boat into the center of a quartz tube of a chemical vapor deposition system, and positioning a sapphire substrate 1.5cm above the reaction source material;

b. introducing carrier gas argon, wherein the flow of the argon is controlled at 300 ml/min;

c. when the heating temperature reaches 1100 ℃, oxygen is introduced, the oxygen flow is controlled at 300ml/min, and the growth time is 30 minutes;

d. and closing the oxygen, keeping the flow of the argon, cooling to room temperature, and taking out the sample.

The method comprises the following steps:

a. mixing gallium oxide powder with purity of more than 99.9%, carbon powder and P₂O₅Mixing the powder according to the mass ratio of 6:9:1.5 to prepare a reaction source material, putting the reaction source material into a corundum boat, then putting the corundum boat into the center of a quartz tube of a chemical vapor deposition system, and positioning a sapphire substrate 1.5cm above the reaction source material;

b. introducing carrier gas argon, wherein the flow of the argon is controlled at 300 ml/min;

c. when the heating temperature reaches 1100 ℃, introducing reaction gas oxygen, controlling the flow of the oxygen at 300ml/min, and controlling the growth time at 30 minutes;

d. and closing the oxygen, keeping the flow of the argon, cooling to room temperature, and taking out the sample.

FIG. 5 is phosphorus doped β -Ga prepared in example 2₂O₃Material object of micron lineIn the photograph, as can be seen from fig. 5, the grown micrometer wires have a large density and a length of up to 1cm, and the test shows that the diameter of each micrometer wire is about 40 μm. In addition, EDS spectra gave phosphorus-doped β -Ga prepared in example 2₂O₃The mole percent of phosphorus in the microwire was about 3%. FIG. 6 is a graph of response time of an ultraviolet detector made with microwires prepared in example 2 under 254nm ultraviolet light. It can be seen from FIG. 6 that the dark current value of the ultraviolet device is about I_d=1.56nA, photocurrent was about I_l=3.0 μ a, light to dark current ratio of about (I)_l：I_d）1.92×10³. Compared with the performance of the ultraviolet detector prepared in example 1, the ultraviolet detection performance of a single micrometer ultraviolet detector is obviously enhanced along with the increase of the doping amount of the phosphorus in the micrometer light.

Comparative example

The method comprises the following steps:

a. mixing gallium oxide powder with the purity of more than 99.9% and carbon powder according to the mass ratio of 6:9 to prepare a reaction source material, putting the reaction source material into a corundum boat, then putting the corundum boat into the center of a quartz tube of a chemical vapor deposition system, and positioning a sapphire substrate 1.5cm above the reaction source material;

b. introducing carrier gas argon, wherein the flow of the argon is controlled at 300 ml/min;

c. when the heating temperature reaches 1100 ℃, introducing reaction gas oxygen, controlling the flow of the oxygen at 300ml/min, and controlling the growth time at 30 minutes;

d. and closing the oxygen, keeping the flow of the argon, cooling to room temperature, and taking out the sample.

Similarly, a single micron line is stripped from the bottom of the sample substrate, and electrodes are respectively manufactured at two ends of the single micron line, so that the single gallium oxide micron ultraviolet detector shown in the figure is manufactured.

The response time curve of the single micron line device obtained in the comparative example to 254nm ultraviolet light is shown in fig. 7.

The comparative example is a gallium oxide sample not doped with phosphorus, and the other growth conditions were the same as in examples 1 and 2. FIG. 7 shows that the sample without phosphorus doping has single micrometer ultraviolet rayThe photocurrent value of the detector is about I_l=1.25 μ a, light to dark current ratio of about (I)_l：I_d）6.25×10²By comparison, it can be seen that the values are significantly lower than for phosphorus doped examples 1 and 2.