CN112071942B - Based on NiFe2O4/SiC ultraviolet photodiode and preparation method - Google Patents
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- 229910003264 NiFe2O4 Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 16
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 87
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 57
- 238000004140 cleaning Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 238000007664 blowing Methods 0.000 claims abstract description 7
- 238000004544 sputter deposition Methods 0.000 claims description 214
- 239000013077 target material Substances 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 30
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 30
- 238000005477 sputtering target Methods 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 10
- 229910010293 ceramic material Inorganic materials 0.000 claims description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001294 propane Substances 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 141
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 107
- 239000010408 film Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000010409 thin film Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910018572 CuAlO2 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
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Abstract
The invention discloses a method based on NiFe2O4The invention also discloses a NiFe-based UV photodiode2O4Firstly, cleaning an N-type SiC substrate, and blowing the cleaned N-type SiC substrate to dry for later use; then carrying out intrinsic 4H-SiC homogeneous epitaxial layer growth on the cleaned N-type SiC substrate; carrying out P-type NiFe on the obtained intrinsic 4H-SiC homogeneous epitaxial layer2O4Growing a heteroepitaxial layer; in the obtained P-type NiFe2O4Manufacturing a top electrode on the heteroepitaxial layer; manufacturing a bottom electrode on the lower surface of the N-type SiC substrate to finally form NiFe2O4the/SiC ultraviolet photodiode. The diode of the invention has good photoelectric response, good stability, sensitive response and good repeatability of the processing technology.
Description
Technical Field
The invention belongs to the technical field of ultraviolet photoelectric detection application, and particularly relates to a NiFe-based optical fiber sensor2O4The invention also relates to a NiFe-based UV photodiode2O4A preparation method of a/SiC ultraviolet photodiode.
Background
Ultraviolet detection technology is one of the rapidly developing photoelectric detection technologies in recent years. The ultraviolet detector has important application in missile early warning, water quality monitoring, disaster weather forecast and other aspects. Silicon carbide (4H-SiC) as a representative of third-generation wide bandgap semiconductor materials has the properties of large forbidden band width, high breakdown electric field, high thermal conductivity, high electronic saturation mobility, small dielectric constant and the like, so that the silicon carbide has great application potential in the fields of ultraviolet photoelectric detection devices, power electronics, lasers and the like.
The 4H-SiC PIN type ultraviolet detector has the characteristics of low noise, high photoelectric responsivity and the like. In general, P-type doping of silicon carbide is performed by Al doping, and because ionization energy of Al at room temperature is high, complete ionization of Al at room temperature cannot be performed, so that doping concentration of P-type silicon carbide is not high. And spinel phase P type NiFe2O4The thin film is a semiconductor oxide with excellent photoelectric properties, and according to the current report, the optical band gap is about 2.3eV, and the strong light absorption occurs in the short-wave ultraviolet region. Meanwhile, NiFe is comparable to P-type silicon carbide2O4With a higher hole concentration. The invention designs p-NiFe-based2O4The ultraviolet photodiode of the/n-SiC heterojunction thin film has good photoelectric response, good stability, sensitive reaction, good repeatability of the processing technology and huge application prospect.
Disclosure of Invention
The invention aims to provide a NiFe-based alloy2O4the/SiC ultraviolet photodiode has good photoelectric response, good stability, sensitive reaction and good repeatability of the processing technology.
Another object of the present invention is to provide a NiFe-based alloy2O4A preparation method of a/SiC ultraviolet photodiode.
The first technical scheme adopted by the invention is based on NiFe2O4the/SiC ultraviolet photodiode comprises a top electrode and a bottom electrode, wherein P-type NiFe is sequentially arranged between the top electrode and the bottom electrode from the top electrode to the bottom electrode2O4A film, an I-type SiC film, and an N-type SiC substrate.
The first technical aspect of the present invention is also characterized in that,
the top electrode and the bottom electrode are made of one of Au, Al, Ni, Ti, Cu and Pb metal materials, or alloy or ITO conductive compound containing the metal materials.
The N-type SiC substrate is a doped 4H-SiC single crystal material with the doping concentration of about 1018cm-3(ii) a The type I SiC film is an unintentionally doped 4H-SiC layer, and is dopedThe impurity concentration is about 1015cm-3。
P-type NiFe2O4Film carrier concentration of 1017～1018cm-3。
The second technical scheme adopted by the invention is that the alloy is based on NiFe2O4The preparation method of the/SiC ultraviolet photodiode is implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by blowing for later use;
step 2, carrying out intrinsic 4H-SiC homogeneous epitaxial layer growth on the cleaned N-type SiC substrate in the step 1;
step 3, carrying out P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer obtained in the step 22O4Growing a heteroepitaxial layer;
step 4, obtaining P type NiFe in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer;
step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate, and finally forming NiFe2O4the/SiC ultraviolet photodiode.
The second technical aspect of the present invention is also characterized in that,
the cleaning process in the step 1 comprises the following steps: and cleaning the N-type SiC substrate by using a cleaning solution, a 40% hydrofluoric acid solution, alcohol and deionized water in sequence.
When intrinsic 4H-SiC homogeneous epitaxial layer growth is carried out on the N-type SiC substrate in the step 2, chemical vapor deposition equipment is utilized, silane is used as Si source gas, propane is used as C source gas, and hydrogen is used as carrier gas, wherein the hydrogen flow is 40-60slm, and the C/Si ratio is 1: 1-3: 2, the growth temperature is 1520-1600 ℃, and the growth time is 2-5 min.
Performing P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer in step 32O4Adopting magnetron sputtering equipment during growth of the heteroepitaxial layer, and using NiFe2O4Ceramic material as target material, argon Ar and oxygen O2As sputtering gas, Ar: O in sputtering2The ratio of the sputtering pressure to the sputtering pressure is 10: 1-5: 1, the substrate temperature is 500-600 ℃, and the sputtering pressure is controlledThe pressure is 0.5-5 Pa, the sputtering power is controlled to be 100-200W, the sputtering time is controlled to be 0.1-5 hours, then the material obtained by sputtering is annealed in the air environment, the annealing temperature is 600-700 ℃, the annealing time is 0.5-2 hours, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, adopting a magnetron sputtering method to perform P-type NiFe2O4Making top electrode on the heteroepitaxial layer, firstly using Ti as sputtering target material and making it on P-type NiFe2O4Sputtering the surface of the heteroepitaxial layer to form a Ti layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 0.1-10 Pa, and the sputtering power is controlled to be 100-200W; and then, sputtering Au as a sputtering target material on the surface of the Ti layer to form an Au layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 2-4 Pa, and the sputtering power is 10-20 mW.
Manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method in the step 5, firstly sputtering Ni as a target material on the surface of the N-type 4H-SiC substrate to form a Ni layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 0.1-10 Pa, and the sputtering power is controlled to be 100-200W; and then, sputtering Au as a sputtering target material on the surface of the Ni layer to form an Au layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 2-4 Pa, and the sputtering power is 10-20 mW.
The invention has the beneficial effects that the NiFe2O4The first use of NiFe for SiC UV photodiode2O4a/SiC heterostructure, i.e. fully developed NiFe2O4The material has the characteristic of high light transmittance in a deep ultraviolet region and a visible light region; meanwhile, the SiC material has large forbidden band width and higher critical breakdown electric field intensity, so that the NiFe of the invention2O4the/SiC ultraviolet photodiode has higher voltage withstanding level. Under extreme conditions of high temperature, high pressure, high frequency, high radiation and the like, the NiFe alloy material is adopted2O4The reliability of the novel PIN ultraviolet photoelectric detector of the/SiC ultraviolet photoelectric diode is also greatly improved, and the novel PIN ultraviolet photoelectric detector is more suitable for the extreme environment;
NiFe2O4preparation method of/SiC ultraviolet photodiodeThrough the design of the thickness and the doping concentration of the I-type SiC layer, the width of a space charge region can be increased, photo-generated carriers are increased, and the photoelectric conversion efficiency is improved. Meanwhile, the I-type SiC film can reduce junction capacitance, shorten response time and improve frequency response characteristics; in addition, the increase of the type I SiC thin film can share most of the reverse bias voltage, and is advantageous for suppressing dark current. Thus, NiFe compares to SiC MSM photodetectors2O4the/SiC ultraviolet photodiode has larger photoelectric responsivity and faster response speed.
Drawings
FIG. 1 shows a NiFe alloy of the present invention2O4The structural schematic diagram of the PIN structure ultraviolet photodiode of/SiC;
FIG. 2 shows a NiFe alloy of the present invention2O4A flow chart of a preparation method of the UV photodiode with the/SiC PIN structure.
In the figure, 1. top electrode, 2.P type crystal NiFe2O4The thin film, 3.I type SiC thin film, 4.N type SiC substrate, 5. bottom electrode.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention is based on NiFe2O4the/SiC ultraviolet photodiode comprises a top electrode and a bottom electrode, wherein P-type NiFe is sequentially arranged between the top electrode and the bottom electrode from the top electrode to the bottom electrode as shown in figure 12O4A film, an I-type SiC film, and an N-type SiC substrate.
The top electrode and the bottom electrode are made of one of Au, Al, Ni, Ti, Cu and Pb metal materials, or alloy or ITO conductive compound containing the metal materials.
The N-type SiC substrate is a doped 4H-SiC single crystal material with the doping concentration of about 1018cm-3(ii) a The type I SiC film is an unintentionally doped 4H-SiC layer with the doping concentration of about 1015cm-3。
P-type NiFe2O4Film carrier concentration of 1017～1018cm-3。
The inventionBased on NiFe2O4The preparation method of the/SiC ultraviolet photodiode is shown in a flow chart of fig. 2 and is specifically implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by blowing for later use;
the cleaning process in the step 1 comprises the following steps: and cleaning the N-type SiC substrate by using a cleaning solution, a 40% hydrofluoric acid solution, alcohol and deionized water in sequence.
Step 2, carrying out intrinsic 4H-SiC homogeneous epitaxial layer growth on the cleaned N-type SiC substrate in the step 1;
when intrinsic 4H-SiC homogeneous epitaxial layer growth is carried out on the N-type SiC substrate in the step 2, chemical vapor deposition equipment is utilized, silane is used as Si source gas, propane is used as C source gas, and hydrogen is used as carrier gas, wherein the hydrogen flow is 40-60slm, and the C/Si ratio is 1: 1-3: 2, the growth temperature is 1520-1600 ℃, and the growth time is 2-5 min.
Step 3, carrying out P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer obtained in the step 22O4Growing a heteroepitaxial layer;
performing P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer in step 32O4Adopting magnetron sputtering equipment during growth of the heteroepitaxial layer, and using NiFe2O4Ceramic material as target material, argon Ar and oxygen O2As sputtering gas, Ar: O in sputtering2The proportion is 10: 1-5: 1, the substrate temperature is 500-600 ℃, the sputtering pressure is controlled to be 0.5-5 Pa, the sputtering power is controlled to be 100-200W, the sputtering time is controlled to be 0.1-5 hours, then the material obtained by sputtering is annealed in the air environment, the annealing temperature is 600-700 ℃, the annealing time is 0.5-2 hours, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, obtaining P type NiFe in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer;
step 4, adopting a magnetron sputtering method to perform P-type NiFe2O4Making top electrode on the heteroepitaxial layer, firstly using Ti as sputtering target material and making it on P-type NiFe2O4Heteroepitaxial layer tableForming a Ti layer by surface sputtering, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 0.1-10 Pa, and the sputtering power is controlled to be 100-200W; and then, sputtering Au as a sputtering target material on the surface of the Ti layer to form an Au layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 2-4 Pa, and the sputtering power is 10-20 mW.
Step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate, and finally forming NiFe2O4the/SiC ultraviolet photodiode.
Manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method in the step 5, firstly sputtering Ni as a target material on the surface of the N-type 4H-SiC substrate to form a Ni layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 0.1-10 Pa, and the sputtering power is controlled to be 100-200W; and then, sputtering Au as a sputtering target material on the surface of the Ni layer to form an Au layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 2-4 Pa, and the sputtering power is 10-20 mW.
Example 1
The invention is based on NiFe2O4The preparation method of the/SiC ultraviolet photodiode is shown in a flow chart of fig. 2 and is specifically implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by blowing for later use;
the cleaning process in the step 1 comprises the following steps: and cleaning the N-type SiC substrate by using a cleaning solution, a 40% hydrofluoric acid solution, alcohol and deionized water in sequence.
Step 2, carrying out intrinsic 4H-SiC homogeneous epitaxial layer growth on the cleaned N-type SiC substrate in the step 1;
when intrinsic 4H-SiC homogeneous epitaxial layer growth is carried out on the N-type SiC substrate in the step 2, chemical vapor deposition equipment is utilized, silane is used as Si source gas, propane is used as C source gas, and hydrogen is used as carrier gas, wherein the hydrogen flow is 40-60slm, and the C/Si ratio is 1: 1, the growth temperature is 1520 ℃, and the growth time is 2 min.
Step 3, carrying out P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer obtained in the step 22O4Growing a heteroepitaxial layer;
performing P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer in step 32O4Adopting magnetron sputtering equipment during growth of the heteroepitaxial layer, and using NiFe2O4Ceramic material as target material, argon Ar and oxygen O2As sputtering gas, Ar: O in sputtering2The proportion is 10:1, the substrate temperature is 500 ℃, the sputtering pressure is controlled to be 0.5Pa, the sputtering power is controlled to be 100W, the sputtering time is controlled to be 0.1 hour, then the material obtained by sputtering is annealed in the air environment, the annealing temperature is 600 ℃, the annealing time is 0.5 hour, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, obtaining P type NiFe in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer;
step 4, adopting a magnetron sputtering method to perform P-type NiFe2O4Making top electrode on the heteroepitaxial layer, firstly using Ti as sputtering target material and making it on P-type NiFe2O4Sputtering the surface of the heteroepitaxial layer to form a Ti layer, wherein the sputtering time is controlled to be 0.1 hour, the sputtering pressure is controlled to be 0.1Pa, and the sputtering power is controlled to be 100W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ti layer by sputtering, the sputtering time is controlled to be 0.1 hour, the sputtering pressure is controlled to be 2Pa, and the sputtering power is 10 mW.
Step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate, and finally forming NiFe2O4the/SiC ultraviolet photodiode.
5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method, firstly sputtering Ni as a target material on the surface of the N-type 4H-SiC substrate to form a Ni layer, wherein the sputtering time is controlled to be 0.1 hour, the sputtering pressure is controlled to be 0.1Pa, and the sputtering power is controlled to be 100W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 0.1 hour, the sputtering pressure is controlled to be 2Pa, and the sputtering power is 10 mW.
Example 2
The invention is based on NiFe2O4The preparation method of the/SiC ultraviolet photodiode is shown in a flow chart of fig. 2 and is specifically implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by blowing for later use;
the cleaning process in the step 1 comprises the following steps: and cleaning the N-type SiC substrate by using a cleaning solution, a 40% hydrofluoric acid solution, alcohol and deionized water in sequence.
Step 2, carrying out intrinsic 4H-SiC homogeneous epitaxial layer growth on the cleaned N-type SiC substrate in the step 1;
and 2, when the intrinsic 4H-SiC homogeneous epitaxial layer is grown on the N-type SiC substrate in the step 2, utilizing chemical vapor deposition equipment, taking silane as a Si source gas, propane as a C source gas and hydrogen as a carrier gas, wherein the hydrogen flow is 40-60slm, the C/Si ratio is 3:2, the growth temperature is 1600 ℃, and the growth time is 5 min.
Step 3, carrying out P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer obtained in the step 22O4Growing a heteroepitaxial layer;
performing P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer in step 32O4Adopting magnetron sputtering equipment during growth of the heteroepitaxial layer, and using NiFe2O4Ceramic material as target material, argon Ar and oxygen O2As sputtering gas, Ar: O in sputtering2The proportion is 5:1, the substrate temperature is 600 ℃, the sputtering pressure is controlled to be 5Pa, the sputtering power is controlled to be 100-200W, the sputtering time is controlled to be 5 hours, then the material obtained by sputtering is annealed in the air environment, the annealing temperature is 700 ℃, the annealing time is 2 hours, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, obtaining P type NiFe in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer;
step 4, adopting a magnetron sputtering method to perform P-type NiFe2O4Making top electrode on the heteroepitaxial layer, firstly using Ti as sputtering target material and making it on P-type NiFe2O4Sputtering the surface of the heteroepitaxial layer to form a Ti layer, wherein the sputtering time is controlled to be 2 hours, the sputtering pressure is controlled to be 10Pa, and the sputtering power is controlled to be 200W; then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ti layer by sputtering, the sputtering time is controlled to be 2 hours, and the sputtering pressure is controlled4Pa, and 20mW of sputtering power.
Step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate, and finally forming NiFe2O4the/SiC ultraviolet photodiode.
5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method, firstly sputtering Ni serving as a target material on the surface of the N-type 4H-SiC substrate to form a Ni layer, wherein the sputtering time is controlled to be 2 hours, the sputtering pressure is controlled to be 10Pa, and the sputtering power is controlled to be 200W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 2 hours, the sputtering pressure is controlled to be 4Pa, and the sputtering power is 20 mW.
Example 3
The invention is based on NiFe2O4The preparation method of the/SiC ultraviolet photodiode is shown in a flow chart of fig. 2 and is specifically implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by blowing for later use;
the cleaning process in the step 1 comprises the following steps: and cleaning the N-type SiC substrate by using a cleaning solution, a 40% hydrofluoric acid solution, alcohol and deionized water in sequence.
Step 2, carrying out intrinsic 4H-SiC homogeneous epitaxial layer growth on the cleaned N-type SiC substrate in the step 1;
and 2, when intrinsic 4H-SiC homogeneous epitaxial layer growth is carried out on the N-type SiC substrate in the step 2, utilizing chemical vapor deposition equipment, taking silane as Si source gas, propane as C source gas and hydrogen as carrier gas, wherein the hydrogen flow is 50slm, the C/Si ratio is 2.5:2, the growth temperature is 1580 ℃, and the growth time is 4 min.
Step 3, carrying out P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer obtained in the step 22O4Growing a heteroepitaxial layer;
performing P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer in step 32O4Adopting magnetron sputtering equipment during growth of the heteroepitaxial layer, and using NiFe2O4Ceramic material as target material, argon Ar and oxygen O2As sputtering gas, Ar: O in sputtering2Ratio of 8:1, linerThe bottom temperature is 550 ℃, the sputtering pressure is controlled to be 3Pa, the sputtering power is controlled to be 150W, the sputtering time is controlled to be 3 hours, then the material obtained by sputtering is annealed in the air environment, the annealing temperature is 650 ℃, the annealing time is 1 hour, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, obtaining P type NiFe in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer;
step 4, adopting a magnetron sputtering method to perform P-type NiFe2O4Making top electrode on the heteroepitaxial layer, firstly using Ti as sputtering target material and making it on P-type NiFe2O4Sputtering the surface of the heteroepitaxial layer to form a Ti layer, wherein the sputtering time is controlled to be 1 hour, the sputtering pressure is controlled to be 5Pa, and the sputtering power is controlled to be 150W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ti layer by sputtering, the sputtering time is controlled to be 1 hour, the sputtering pressure is controlled to be 3Pa, and the sputtering power is 15 mW.
Step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate, and finally forming NiFe2O4the/SiC ultraviolet photodiode.
Step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method, firstly sputtering Ni as a target material on the surface of the N-type 4H-SiC substrate to form a Ni layer, wherein the sputtering time is controlled to be 1 hour, the sputtering pressure is controlled to be 5Pa, and the sputtering power is controlled to be 150W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 1 hour, the sputtering pressure is controlled to be 3Pa, and the sputtering power is 15 mW.
Example 4
NiFe2O4The preparation method of the/SiC ultraviolet photodiode is implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by using nitrogen for later use, wherein the cleaning process comprises the following steps: cleaning a sample by using a cleaning solution, hydrofluoric acid, alcohol and deionized water step by step;
step 2, growing an intrinsic SiC homogeneous epitaxial layer on the N-type SiC substrate cleaned in the step 1 by using a chemical vapor deposition method, wherein silane and propane are used as Si source gas and C source gas, hydrogen is used as carrier gas, the hydrogen flow is 60slm, the C/Si ratio is 2.4:2, the growth temperature is 1520 ℃, and the growth time is controlled to be about 3 min;
step 3, performing P-type NiFe on the intrinsic SiC homogeneous epitaxial layer obtained in the step 2 by adopting a magnetron sputtering method2O4And growing the heteroepitaxial layer. When sputtering, NiFe is used2O4The ceramic material is used as a target material, argon and oxygen are used as sputtering gases, and Ar is O during sputtering2The ratio of the deposition time to the substrate temperature is 10:1, the substrate temperature is 550 ℃, the deposition pressure is controlled to be 1Pa, the sputtering power is controlled to be 125W, the deposition time is controlled to be 1 hour, then the sample obtained by sputtering is annealed in the air environment, the annealing temperature is 600 ℃, the annealing time is 1 hour, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, adopting a magnetron sputtering method to obtain the P-type NiFe obtained in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer, firstly, taking Ti as a target material, controlling the sputtering time to be 0.1 hour, controlling the sputtering pressure to be 10Pa and controlling the sputtering power to be 100W; then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 0.1 hour, the sputtering pressure is controlled to be 4Pa, and the sputtering power is 20 mW;
step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method, firstly, taking Ni as a target material, controlling the sputtering time to be 2 hours, controlling the sputtering pressure to be 0.1Pa, and controlling the sputtering power to be 200W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 0.1 hour, the sputtering pressure is controlled to be 4Pa, and the sputtering power is 20 mW. Finally forming the CuAlO2the/SiC ultraviolet photodiode.
Example 5
NiFe2O4The preparation method of the/SiC ultraviolet photodiode is implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by using nitrogen for later use, wherein the cleaning process comprises the following steps: cleaning a sample by using a cleaning solution, hydrofluoric acid, alcohol and deionized water step by step;
step 2, growing an intrinsic SiC homogeneous epitaxial layer on the N-type SiC substrate cleaned in the step 1 by using a chemical vapor deposition method, wherein silane and propane are used as Si source gas and C source gas, hydrogen is used as carrier gas, the hydrogen flow is 60slm, the C/Si ratio is 2.4:2, the growth temperature is 1540 ℃, and the growth time is controlled to be about 3 min;
step 3, performing P-type NiFe on the intrinsic SiC homogeneous epitaxial layer obtained in the step 2 by adopting a magnetron sputtering method2O4And growing the heteroepitaxial layer. When sputtering, NiFe is used2O4The ceramic material is used as a target material, argon and oxygen are used as sputtering gases, and Ar is O during sputtering2The ratio of the temperature to the temperature of the substrate is 10:1, the temperature of the substrate is 550 ℃, the sputtering pressure is controlled to be 1Pa, the sputtering power is controlled to be 125W, the sputtering time is controlled to be 1 hour, then the sample obtained by sputtering is annealed in the air environment, the annealing temperature is 600 ℃, the annealing time is 1 hour, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, adopting a magnetron sputtering method to obtain the P-type NiFe obtained in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer, firstly, taking Ti as a target material, controlling the sputtering time to be 0.1 hour, controlling the sputtering pressure to be 10Pa and controlling the sputtering power to be 100W; then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 2 hours, the sputtering pressure is controlled to be 2Pa, and the sputtering power is 10 mW;
step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method, firstly, taking Ni as a target material, controlling the sputtering time to be 0.1 hour, controlling the sputtering pressure to be 10Pa, and controlling the sputtering power to be 100W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 2 hours, the sputtering pressure is controlled to be 2Pa, and the sputtering power is 10 mW. Finally forming the CuAlO2the/SiC ultraviolet photodiode.
Example 6
NiFe2O4The preparation method of the/SiC ultraviolet photodiode is implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by using nitrogen for later use, wherein the cleaning process comprises the following steps: cleaning a sample by using a cleaning solution, hydrofluoric acid, alcohol and deionized water step by step;
step 2, growing an intrinsic SiC homogeneous epitaxial layer on the N-type SiC substrate cleaned in the step 1 by using a chemical vapor deposition method, wherein silane and propane are used as Si source gas and C source gas, hydrogen is used as carrier gas, the hydrogen flow is 60slm, the C/Si ratio is 2.4:2, the growth temperature is 1560 ℃, and the growth time is controlled to be about 3 min;
step 3, performing P-type NiFe on the intrinsic SiC homogeneous epitaxial layer obtained in the step 2 by adopting a magnetron sputtering method2O4And growing the heteroepitaxial layer. When sputtering, NiFe is used2O4The ceramic material is used as a target material, argon and oxygen are used as sputtering gases, and Ar is O during sputtering2The ratio of the time to the temperature of the substrate is 5:1, the substrate temperature is 550 ℃, the sputtering pressure is controlled to be 1Pa, the sputtering power is controlled to be 125W, the sputtering time is controlled to be 1 hour, then the sample obtained by sputtering is annealed in the air environment, the annealing temperature is 600 ℃, the annealing time is 1 hour, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, adopting a magnetron sputtering method to obtain the P-type NiFe obtained in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer, firstly, taking Ti as a target material, controlling the sputtering time to be 0.5 hour, controlling the sputtering pressure to be 5Pa and controlling the sputtering power to be 110W; then, Au is used as a sputtering target material to form an Au layer on the surface of the Ni layer in a sputtering mode, the sputtering time is controlled to be 1 hour, the sputtering pressure is controlled to be 3Pa, and the sputtering power is 15 mW;
step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method, firstly, taking Ni as a target material, controlling the sputtering time to be 0.5 hour, controlling the sputtering pressure to be 5Pa, and controlling the sputtering power to be 100W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 1.5 hours, the sputtering pressure is controlled to be 3Pa, and the sputtering power is 15 mW. Finally forming the CuAlO2the/SiC ultraviolet photodiode.
Example 7
NiFe2O4SiC ultraviolet photoelectric deviceThe preparation method of the polar tube is implemented according to the following steps:
step 1, cleaning an N-type SiC substrate, and drying the cleaned N-type SiC substrate by using nitrogen for later use, wherein the cleaning process comprises the following steps: cleaning a sample by using a cleaning solution, hydrofluoric acid, alcohol and deionized water step by step;
step 2, growing an intrinsic SiC homogeneous epitaxial layer on the N-type SiC substrate cleaned in the step 1 by using a chemical vapor deposition method, wherein silane and propane are used as Si source gas and C source gas, hydrogen is used as carrier gas, the hydrogen flow is 60slm, the C/Si ratio is 2.4:2, the growth temperature is 1580 ℃, and the growth time is controlled to be about 3 min;
step 3, performing P-type NiFe on the intrinsic SiC homogeneous epitaxial layer obtained in the step 2 by adopting a magnetron sputtering method2O4And growing the heteroepitaxial layer. When sputtering, NiFe is used2O4The ceramic material is used as a target material, argon and oxygen are used as sputtering gases, and Ar is O during sputtering2The ratio of the time to the temperature is 5:1, the substrate temperature is 580 ℃, the sputtering pressure is controlled to be 1Pa, the sputtering power is controlled to be 125W, the sputtering time is controlled to be 1 hour, then the sample obtained by sputtering is annealed in the air environment, the annealing temperature is 650 ℃, the annealing time is 1 hour, and the P-type NiFe is obtained2O4A heteroepitaxial layer.
Step 4, adopting a magnetron sputtering method to obtain the P-type NiFe obtained in the step 32O4Manufacturing a top electrode on the heteroepitaxial layer, firstly, taking Ti as a target material, controlling the sputtering time to be 1.5 hours, controlling the sputtering pressure to be 6Pa and controlling the sputtering power to be 150W; then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 1.5 hours, the sputtering pressure is controlled to be 3Pa, and the sputtering power is 15 mW;
step 5, manufacturing a bottom electrode on the lower surface of the N-type SiC substrate by adopting a magnetron sputtering method, firstly, taking Ni as a target material, controlling the sputtering time to be 2 hours, controlling the sputtering pressure to be 4Pa, and controlling the sputtering power to be 130W; and then, Au is taken as a sputtering target material to form an Au layer on the surface of the Ni layer by sputtering, the sputtering time is controlled to be 0.8 hour, the sputtering pressure is controlled to be 2.5Pa, and the sputtering power is 17 mW.
Claims (2)
1. Based on NiFe2O4the/SiC ultraviolet photodiode is characterized by comprising a top electrode (1) and a bottom electrode (5), wherein P-type NiFe is sequentially arranged between the top electrode (1) and the bottom electrode (5) from the top electrode (1) to the bottom electrode (5)2O4A film (2), an I-type SiC film (3) and an N-type SiC substrate (4); the top electrode (1) and the bottom electrode (5) are made of one of Au, Al, Ni, Ti, Cu and Pb metal materials, or alloy or ITO conductive compound containing the metal materials, the N-type SiC substrate (4) is a doped 4H-SiC single crystal material, and the doping concentration is 1018cm-3(ii) a The type I SiC film (3) is an unintentionally doped 4H-SiC layer with the doping concentration of 1015cm-3Said P type NiFe2O4The film (2) has a carrier concentration of 1017～1018cm-3。
2. Based on NiFe2O4The preparation method of the/SiC ultraviolet photodiode is characterized by comprising the following steps:
step 1, cleaning an N-type SiC substrate (4), and drying the cleaned substrate by blowing for later use; the cleaning process in the step 1 comprises the following steps: cleaning the N-type SiC substrate (4) by sequentially using a cleaning solution, a 40% hydrofluoric acid solution, alcohol and deionized water;
step 2, growing an intrinsic 4H-SiC homogeneous epitaxial layer on the N-type SiC substrate (4) cleaned in the step 1; when intrinsic 4H-SiC homogeneous epitaxial layer growth is carried out on the N-type SiC substrate (4) in the step 2, a chemical vapor deposition device is utilized, silane is used as a Si source gas, propane is used as a C source gas, and hydrogen is used as a carrier gas, wherein the hydrogen flow is 40-60slm, and the C/Si ratio is 1: 1-3: 2, the growth temperature is 1520-1600 ℃, and the growth time is 2-5 min;
step 3, carrying out P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer obtained in the step 22O4Growing a heteroepitaxial layer; performing P-type NiFe on the intrinsic 4H-SiC homogeneous epitaxial layer in step 32O4Adopting magnetron sputtering equipment during growth of the heteroepitaxial layer, and using NiFe2O4The ceramic material is used as a target material,with argon Ar and oxygen O2As sputtering gas, Ar: O in sputtering2The proportion is 10: 1-5: 1, the substrate temperature is 500-600 ℃, the sputtering pressure is controlled to be 0.5-5 Pa, the sputtering power is controlled to be 100-200W, the sputtering time is controlled to be 0.1-5 hours, then the material obtained by sputtering is annealed in the air environment, the annealing temperature is 600-700 ℃, the annealing time is 0.5-2 hours, and the P-type NiFe is obtained2O4A heteroepitaxial layer;
step 4, obtaining P type NiFe in the step 32O4Manufacturing a top electrode (1) on the heteroepitaxial layer; step 4, adopting a magnetron sputtering method to perform P-type NiFe2O4Making top electrode on the heteroepitaxial layer, firstly using Ti as sputtering target material and making it on P-type NiFe2O4Sputtering the surface of the heteroepitaxial layer to form a Ti layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 0.1-10 Pa, and the sputtering power is controlled to be 100-200W; then, Au is used as a sputtering target material to sputter on the surface of the Ti layer to form an Au layer, the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 2-4 Pa, and the sputtering power is 10-20 mW;
step 5, manufacturing a bottom electrode (5) on the lower surface of the N-type SiC substrate (4), and finally forming NiFe2O4a/SiC ultraviolet photodiode, wherein a bottom electrode (5) is manufactured on the lower surface of the N-type SiC substrate (4) by adopting a magnetron sputtering method in step 5, Ni is firstly used as a target material to be sputtered on the surface of the N-type 4H-SiC substrate to form a Ni layer, the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 0.1-10 Pa, and the sputtering power is controlled to be 100-200W; and then, sputtering Au as a sputtering target material on the surface of the Ni layer to form an Au layer, wherein the sputtering time is controlled to be 0.1-2 hours, the sputtering pressure is controlled to be 2-4 Pa, and the sputtering power is 10-20 mW.
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