CN108914086B - Iron-doped diamond diluted magnetic semiconductor and preparation method thereof - Google Patents
Iron-doped diamond diluted magnetic semiconductor and preparation method thereof Download PDFInfo
- Publication number
- CN108914086B CN108914086B CN201810786224.8A CN201810786224A CN108914086B CN 108914086 B CN108914086 B CN 108914086B CN 201810786224 A CN201810786224 A CN 201810786224A CN 108914086 B CN108914086 B CN 108914086B
- Authority
- CN
- China
- Prior art keywords
- iron
- doped diamond
- cavity
- magnetic semiconductor
- diamond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 82
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 82
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 54
- 239000004065 semiconductor Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 35
- 238000000151 deposition Methods 0.000 claims description 29
- 230000008021 deposition Effects 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 15
- 239000012159 carrier gas Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 230000006911 nucleation Effects 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 8
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000630 rising effect Effects 0.000 abstract description 4
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 235000012431 wafers Nutrition 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/274—Diamond only using microwave discharges
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/276—Diamond only using plasma jets
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N50/00—Galvanomagnetic devices
- H10N50/80—Constructional details
- H10N50/85—Magnetic active materials
Abstract
The invention relates to an iron-doped diamond diluted magnetic semiconductor and a preparation method thereof. The invention takes ferric acetylacetonate as an iron source for the first time, introduces the ferric acetylacetonate through volatilized absolute ethyl alcohol, adopts a microwave plasma chemical vapor deposition method to prepare the diluted magnetic diamond semiconductor, and successfully grows the diamond with ferromagnetic effect at room temperature. And it was found that the magnetic strength of diamond showed a rising phenomenon as the amount of the iron source was increased. The research aiming at the rare magnetic semiconductor is beneficial to exploring the rare magnetic semiconductor characteristics of the iron-doped diamond to the maximum extent and exploring more possibilities of magnetic doping of the diamond.
Description
Technical Field
The invention belongs to the field of diluted magnetic semiconductor preparation, and particularly relates to an iron-doped diamond with diluted magnetic semiconductor characteristics at room temperature and a preparation method thereof.
Background
The diluted magnetic semiconductor is a spin source with important prospect, and is an important supporting material of a new generation of spin devices. Just half a century ago, a computer with limited functionality was large enough to fill the entire room, and today, our pockets hold powerful "electronics". The pursuit of miniaturized and more powerful electronic devices is endless, however, heat dissipation and technical difficulties, such as tunneling, have affected the further development of conventional silicon-based transistors. Researchers continue to seek a solution where a very promising approach is spintronics, because less energy can be used to control electron spin flip as compared to charge movement. However, Schmidt et al have used transition metals (e.g., Ni, Co) as spin sources for injection into semiconductor channels, where the efficiency of spin injection is very low (less than 5%) and difficult to detect due to mismatch, etc.; and the diluted magnetic semiconductor with spin polarization obtained by doping with a magnetic element has very high spin injection efficiency (higher than 90%). Therefore, the magnetic element doped semiconductor is the most widely studied object, such as the reported diluted magnetic semiconductor of magnetic ion Mn doped GaAs, GaN and the like and the ZnO based diluted magnetic semiconductor doped with transition metal element.
The diamond has excellent performances of forbidden bandwidth, high breakdown field strength, high carrier mobility, low dielectric constant, good heat conductivity and the like, has the characteristics of stable chemical performance, high hardness, high wear resistance, strong radiation resistance and the like, is a high-temperature and high-power wide-forbidden-band semiconductor material with development prospect, and is known as a first-choice material of fourth-generation semiconductors. Therefore, the method has important significance in exploring the preparation process of the iron-doped diamond film. However, there is no literature or patent report of such diamond, which is difficult to obtain by conventional methods because of the complex growth conditions and the sensitivity to growth parameters.
Disclosure of Invention
The invention aims to solve the technical problem of providing an iron-doped diamond diluted magnetic semiconductor and a preparation method thereof, aiming at the defects of the prior art, iron is successfully doped into a diamond film, the magnetic strength of the diamond film shows a rising change trend along with the increase of the iron doping amount, and diamond with diluted magnetic semiconductor characteristics at room temperature can be obtained.
The technical scheme adopted by the invention for solving the problems is as follows:
the preparation method of the iron-doped diamond diluted magnetic semiconductor comprises the steps of taking iron acetylacetonate as an iron source and absolute ethyl alcohol as a carbon source, introducing the iron acetylacetonate into a microwave plasma chemical vapor deposition device through the absolute ethyl alcohol, and growing an iron-doped diamond film on a substrate to realize the introduction of iron elements into the diamond film so as to obtain the iron-doped diamond diluted magnetic semiconductor.
According to the scheme, the substrate is subjected to ultrasonic cleaning by using a diamond suspension in advance, so that the surface energy of the silicon wafer is increased, and diamond nucleation is facilitated. For example, the substrate is selected from silicon wafers and the like.
According to the scheme, ferric acetylacetonate is dissolved in absolute ethyl alcohol, and the solution is heated and volatilized to be introduced into a deposition cavity of a microwave plasma chemical vapor deposition device. Wherein the concentration of the ferric acetylacetonate in the absolute ethyl alcohol is 0.25-2.5 g/L; the heating and volatilization can be carried out by heating the mixed solution of ferric acetylacetonate and absolute ethyl alcohol in a water bath, wherein the heating temperature range is 35-50 ℃.
Further preferably, the ferric acetylacetonate is dissolved in the absolute ethyl alcohol and is introduced into the deposition cavity of the microwave plasma chemical vapor deposition device by heating and volatilizing and carrying an inert carrier gas. Wherein the flow rate of the inert carrier gas is 5-10 sccm, and the inert carrier gas can be rare gas such as argon.
According to the scheme, the technological parameters of the microwave plasma chemical vapor deposition device are as follows: and introducing hydrogen into the deposition cavity, adjusting the microwave power and the pressure in the vacuum cavity, and exciting to generate plasma, wherein the hydrogen flow is 100-200 sccm, the microwave power is 700-1100W, the working pressure is 10-12 kPa, the substrate temperature is 700-900 ℃, and the reaction time is 6-28 h.
Preferably, the invention also provides a more specific preparation method of the iron-doped diamond diluted magnetic semiconductor, which mainly comprises the following steps:
1) substrate pretreatment: the substrate (such as a silicon wafer and the like) is subjected to ultrasonic cleaning by using the diamond suspension, so that the surface energy of the substrate is increased, and diamond nucleation is facilitated;
2) preparing a precursor solution: dissolving ferric acetylacetonate into absolute ethyl alcohol in a conical flask to obtain a precursor solution, wherein the ferric acetylacetonate is used as an iron source, and the absolute ethyl alcohol is used as a carbon source;
3) preparing a device: putting a substrate into a deposition cavity of a microwave plasma chemical vapor deposition device, vacuumizing the cavity (till the vacuum degree is 10-100Pa), introducing hydrogen into the cavity, adjusting the microwave power and the air pressure in a vacuum cavity, and exciting to generate plasma, wherein the used process parameters are as follows: the hydrogen flow is 100-200 sccm, the microwave power is 700-1100W, the working pressure is 10-12 kPa, and the substrate temperature is 700-900 ℃;
4) heating the precursor solution in water bath at the temperature of 35-50 ℃ to increase the volatilization of the solution; and (3) introducing carrier gas, wherein the carrier gas pipeline flows through the precursor solution, so that the volatilization of the solution can be increased, the transmission of the ferric acetylacetonate is facilitated, and the used technological parameters are as follows: the argon flow is 0-10sccm, and the concentration of the mixed solution of ferric acetylacetonate and absolute ethyl alcohol is 0.25-2.5 g/L;
5) adjusting a vacuum fine-tuning valve of the deposition cavity to keep the air pressure in the deposition cavity within a certain range and stabilize the state of the plasma, wherein the used process parameters are as follows: the pressure in the cavity is 10-12 kPa, and the reaction time is 6-28h, so that the iron-doped diamond film is obtained.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes ferric acetylacetonate as an iron source for the first time, introduces the ferric acetylacetonate through volatilized absolute ethyl alcohol, adopts a microwave plasma chemical vapor deposition method to prepare the diluted magnetic diamond film, and successfully grows the semiconductor diamond film with the ferromagnetic effect at room temperature. The method has the advantages that the introduction amount of the iron source is easy to control; and the gas phase components are reduced by adopting microwave plasma, the gas is easy to dissociate due to high microwave energy density and high power, and the radicals have high activity and are beneficial to doping of iron.
Secondly, the magnetic strength of the iron-doped diamond film prepared by the method of the invention shows a rising phenomenon along with the increase of the iron doping amount, which is beneficial to exploring the intrinsic physical properties of the iron-doped diamond film to the maximum extent and exploring more possibilities of magnetic doping of the diamond.
Moreover, the plasma is covered above the substrate in the method, so that sufficient temperature is provided for the substrate, and the self-heating mode of the plasma promotes the deposition of radicals on the surface of the silicon wafer; in addition, the method of the invention also has the advantages of adjustable microwave power, lower deposition pressure and the like.
Drawings
FIG. 1 is an optical photograph of an iron-doped diamond diluted magnetic semiconductor prepared according to the present invention.
FIG. 2 is a schematic structural diagram of an apparatus for manufacturing an iron-doped diamond film according to the present invention, wherein 1, a microwave source; 2. an air pumping port of a vacuum pump; 3. a vacuum chamber; 4. a water bath heating device; 5. a substrate stage; 6. a cylindrical quartz tube; 7. anhydrous ethanol solution with dissolved ferric acetylacetonate; 8. an argon bottle; 9. a gas cylinder pressure reducing valve; 10. a hydrogen cylinder.
FIG. 3 is an electron spectrum test chart of sample # 2 in the example.
FIG. 4 is an electron spectrum test chart of sample # 3 in the example.
FIG. 5 is an electron spectrum test chart of sample # 5 in the example.
Detailed Description
The present invention will be further described with reference to the following drawings and examples, but the present invention is not limited to the following examples.
The invention provides a device for preparing an iron-doped diamond diluted magnetic semiconductor, but the device is not limited to realize the technical scheme of the invention, and any device capable of realizing the technical scheme of the invention can be used.
As shown in fig. 2, in the following examples, an apparatus for manufacturing an iron-doped diamond film includes: 1. a microwave source; 2. an air pumping port of a vacuum pump; 3. a vacuum chamber; 4. a water bath heating device; 5. a substrate stage; 6. a cylindrical quartz tube; 7. anhydrous ethanol solution with dissolved ferric acetylacetonate; 8. an argon bottle; 9. a gas cylinder pressure reducing valve; 10. a hydrogen cylinder. The vacuum pump extraction opening 2 is connected with a vacuum pump (used for extracting air in the vacuum chamber 3 to vacuum) through a vacuum pipeline, and a vacuum fine adjustment valve is arranged on the vacuum pipeline; the hydrogen pipeline is connected with a vacuum chamber 3, the vacuum chamber 3 is cylindrical, and a cylindrical quartz tube 6 is arranged in the middle of the circumferential surface of the vacuum chamber 3 (the position close to a silicon wafer is positioned on a substrate table in the center of the vacuum chamber 3); 2.45GHz microwaves enter the vacuum chamber 3 from the microwave source 1 through the quartz tube 6 for coupling, and the gas absorbs microwave energy to ionize to generate plasma after entering the cavity; the iron acetylacetonate is carried into the vacuum chamber 3 through a pipe by the volatilized ethanol and argon gas.
Example 1
The preparation method of the iron-doped diamond diluted magnetic semiconductor comprises the following specific steps:
1) substrate pretreatment: the substrate (silicon wafer) is ultrasonically cleaned by using the diamond suspension liquid, so that the surface energy of the substrate is increased, and diamond nucleation is facilitated;
2) preparing a precursor solution: dissolving 0.1g of ferric acetylacetonate into 400ml of absolute ethyl alcohol in a conical flask to obtain a precursor solution, wherein the ferric acetylacetonate is used as an iron source and the absolute ethyl alcohol is used as a carbon source;
3) preparing a device: in a deposition cavity of a microwave plasma chemical vapor deposition device, a silicon wafer is placed at the center position above a substrate table, the cavity is vacuumized (until the vacuum degree is 10-100Pa), hydrogen is introduced into the cavity, the microwave power and the air pressure in the vacuum cavity are adjusted, and plasma is generated by excitation, wherein the used process parameters are as follows: the hydrogen flow is 200sccm, the microwave power is 800W, the working air pressure is 11kPa, and the substrate temperature is 800 ℃;
4) carrying out water bath constant temperature heating on the conical flask containing the precursor solution, wherein the heating temperature is 45 ℃, and the argon flow is 0 sccm;
5) adjusting a vacuum fine-tuning valve of the deposition cavity to keep the air pressure in the deposition cavity within a certain range and stabilize the state of the plasma, wherein the used process parameters are as follows: and (3) closing the microwave source, the gas source, the power source and the cooling water when the pressure in the cavity is 10-12 kPa and the reaction time is 6h, and taking out the sample after the cavity is cooled to obtain the iron-doped diamond film (marked as a No. 1 sample).
The magnetic properties of the iron-doped diamond film were tested by the comprehensive physical property measurement system PPMS, and after the test, the sample # 1 was found to have no magnetism.
Example 2
The preparation method of the iron-doped diamond diluted magnetic semiconductor comprises the following specific steps:
1) substrate pretreatment: the substrate (silicon wafer) is ultrasonically cleaned by using the diamond suspension liquid, so that the surface energy of the substrate is increased, and diamond nucleation is facilitated;
2) preparing a precursor solution: dissolving 0.2g of ferric acetylacetonate into 400ml of absolute ethyl alcohol in a conical flask to obtain a precursor solution, wherein the ferric acetylacetonate is used as an iron source and the absolute ethyl alcohol is used as a carbon source;
3) preparing a device: in a deposition cavity of a microwave plasma chemical vapor deposition device, a silicon wafer is placed at the center position above a substrate table, the cavity is vacuumized (until the vacuum degree is 10-100Pa), hydrogen is introduced into the cavity, the microwave power and the air pressure in the vacuum cavity are adjusted, and plasma is generated by excitation, wherein the used process parameters are as follows: the hydrogen flow is 200sccm, the microwave power is 800W, the working air pressure is 11kPa, and the substrate temperature is 800 ℃;
4) carrying out water bath constant temperature heating on the conical flask containing the precursor solution, wherein the heating temperature is 45 ℃, and introducing argon with the flow rate of 5 sccm;
5) adjusting a vacuum fine-tuning valve of the deposition cavity to keep the air pressure in the deposition cavity within a certain range and stabilize the state of the plasma, wherein the used process parameters are as follows: and (3) closing the microwave source, the gas source, the power source and the cooling water when the pressure in the cavity is 10-12 kPa and the reaction time is 10h, and taking out the sample after the cavity is cooled to obtain the iron-doped diamond film (marked as a #2 sample).
The magnetic properties of the iron-doped diamond film were tested by the comprehensive physical property measurement system PPMS, and after the test, the sample # 2 was found to have no magnetism. FIG. 3 is an electron spectrum test chart of the sample # 2, which has an iron content of 0.054 wt%.
Example 3
The preparation method of the iron-doped diamond diluted magnetic semiconductor comprises the following specific steps:
1) substrate pretreatment: the substrate (silicon wafer) is ultrasonically cleaned by using the diamond suspension liquid, so that the surface energy of the substrate is increased, and diamond nucleation is facilitated;
2) preparing a precursor solution: dissolving 0.2g of ferric acetylacetonate into 400ml of absolute ethyl alcohol in a conical flask to obtain a precursor solution, wherein the ferric acetylacetonate is used as an iron source and the absolute ethyl alcohol is used as a carbon source;
3) preparing a device: in a deposition cavity of a microwave plasma chemical vapor deposition device, a silicon wafer is placed at the center position above a substrate table, the cavity is vacuumized (until the vacuum degree is 10-100Pa), hydrogen is introduced into the cavity, the microwave power and the air pressure in the vacuum cavity are adjusted, and plasma is generated by excitation, wherein the used process parameters are as follows: the hydrogen flow is 200sccm, the microwave power is 800W, the working air pressure is 11kPa, and the substrate temperature is 800 ℃;
4) carrying out water bath constant temperature heating on the conical flask containing the precursor solution, wherein the heating temperature is 45 ℃, and introducing argon with the flow rate of 5 sccm;
5) adjusting a vacuum fine-tuning valve of the deposition cavity to keep the air pressure in the deposition cavity within a certain range and stabilize the state of the plasma, wherein the used process parameters are as follows: and (3) closing the microwave source, the gas source, the power source and the cooling water when the pressure in the cavity is 10-12 kPa and the reaction time is 15h, cooling the cavity, and taking out the sample to obtain the iron-doped diamond film (namely the iron-doped diamond diluted magnetic semiconductor, marked as sample # 3).
The magnetic property of the iron-doped diamond film is tested by a PPMS (comprehensive physical property measurement system), and after the test, the No. 3 sample shows weak ferromagnetism at low temperature.
FIG. 4 is an electron spectrum test chart of the sample # 3, which has an iron content of 0.199 wt%.
Example 4
The preparation method of the iron-doped diamond diluted magnetic semiconductor comprises the following specific steps:
1) substrate pretreatment: the substrate (silicon wafer) is ultrasonically cleaned by using the diamond suspension liquid, so that the surface energy of the substrate is increased, and diamond nucleation is facilitated;
2) preparing a precursor solution: dissolving 0.4g of ferric acetylacetonate into 400ml of absolute ethyl alcohol in a conical flask to obtain a precursor solution, wherein the ferric acetylacetonate is used as an iron source and the absolute ethyl alcohol is used as a carbon source;
3) preparing a device: in a deposition cavity of a microwave plasma chemical vapor deposition device, a silicon wafer is placed at the center position above a substrate table, the cavity is vacuumized (until the vacuum degree is 10-100Pa), hydrogen is introduced into the cavity, the microwave power and the air pressure in the vacuum cavity are adjusted, and plasma is generated by excitation, wherein the used process parameters are as follows: the hydrogen flow is 200sccm, the microwave power is 800W, the working air pressure is 11kPa, and the substrate temperature is 800 ℃;
4) carrying out water bath constant temperature heating on the conical flask containing the precursor solution, wherein the heating temperature is 45 ℃, and introducing argon with the flow rate of 5 sccm;
5) adjusting a vacuum fine-tuning valve of the deposition cavity to keep the air pressure in the deposition cavity within a certain range and stabilize the state of the plasma, wherein the used process parameters are as follows: and (3) closing the microwave source, the gas source, the power supply and the cooling water when the pressure in the cavity is 10-12 kPa and the reaction time is 20h, cooling the cavity, and taking out the sample to obtain the iron-doped diamond film (namely the iron-doped diamond diluted magnetic semiconductor, marked as sample No. 4).
The magnetic properties of the iron-doped diamond film were tested by the comprehensive physical property measurement system PPMS, and after the test, the sample # 4 was found to exhibit weak ferromagnetism at low temperature.
Example 5
The preparation method of the iron-doped diamond diluted magnetic semiconductor comprises the following specific steps:
1) substrate pretreatment: the substrate (silicon wafer) is ultrasonically cleaned by using the diamond suspension liquid, so that the surface energy of the substrate is increased, and diamond nucleation is facilitated;
2) preparing a precursor solution: dissolving 0.5g of ferric acetylacetonate into 400ml of absolute ethyl alcohol in a conical flask to obtain a precursor solution, wherein the ferric acetylacetonate is used as an iron source and the absolute ethyl alcohol is used as a carbon source;
3) preparing a device: in a deposition cavity of a microwave plasma chemical vapor deposition device, a silicon wafer is placed at the center position above a substrate table, the cavity is vacuumized (until the vacuum degree is 10-100Pa), hydrogen is introduced into the cavity, the microwave power and the air pressure in the vacuum cavity are adjusted, and plasma is generated by excitation, wherein the used process parameters are as follows: the hydrogen flow is 200sccm, the microwave power is 800W, the working air pressure is 11kPa, and the substrate temperature is 800 ℃;
4) carrying out water bath constant temperature heating on the conical flask containing the precursor solution, wherein the heating temperature is 45 ℃, and introducing argon with the flow rate of 5 sccm;
5) adjusting a vacuum fine-tuning valve of the deposition cavity to keep the air pressure in the deposition cavity within a certain range and stabilize the state of the plasma, wherein the used process parameters are as follows: and (3) closing the microwave source, the gas source, the power source and the cooling water when the pressure in the cavity is 10-12 kPa and the reaction time is 28h, cooling the cavity, and taking out the sample to obtain the iron-doped diamond film (namely the iron-doped diamond diluted magnetic semiconductor, marked as sample No. 5).
The magnetic property of the iron-doped diamond film is tested by a comprehensive physical property measurement system PPMS, and after the test, the sample # 5 has a ferromagnetic effect at room temperature, and the forbidden bandwidth is 1.49 eV.
FIG. 5 is an electron spectrum test chart of the sample # 5, which has an iron content of 0.46 wt%.
Examples 1-5 above prepared 5 samples with detailed parameters as shown in table 1. As can be seen from Table 1: compared with the embodiment 1, the argon gas in the embodiments 2 to 5 not only facilitates the transmission of the ferric acetylacetonate, but also can increase the volatilization of the solution, which can increase the introduction amount of the iron; in 5 samples, the dosage of the iron source is increased in sequence along with the increasing of the concentration of the precursor solution and the time, and the magnetic strength of the diamond film shows a rising phenomenon along with the increase of the dosage of the iron source by combining the magnetic test results of the samples. However, as the content of iron in examples 1 to 5 increased, the impurity phases in the diamond samples increased accordingly, and the resulting sample No. 5 having diluted magnetic semiconductor characteristics at room temperature was still a high-quality diamond sample.
TABLE 1
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (9)
1. The preparation method of the iron-doped diamond diluted magnetic semiconductor is characterized in that ferric acetylacetonate is used as an iron source, absolute ethyl alcohol is used as a carbon source, the ferric acetylacetonate is introduced into a microwave plasma chemical vapor deposition device through the absolute ethyl alcohol, and an iron-doped diamond film grows on a substrate to obtain the iron-doped diamond diluted magnetic semiconductor;
the technological parameters of the microwave plasma chemical vapor deposition device are as follows: and introducing hydrogen into the deposition cavity, adjusting the microwave power and the pressure in the vacuum cavity, and exciting to generate plasma, wherein the hydrogen flow is 100-200 sccm, the microwave power is 700-1100W, the working pressure is 10-12 kPa, the substrate temperature is 700-900 ℃, and the reaction time is 6-28 h.
2. The method for preparing an iron-doped diamond diluted magnetic semiconductor according to claim 1, wherein iron acetylacetonate is dissolved in absolute ethyl alcohol, and the solution is heated to volatilize and introduced into a deposition cavity of a microwave plasma chemical vapor deposition device.
3. The method for preparing an iron-doped diamond diluted magnetic semiconductor according to claim 1, wherein iron acetylacetonate is dissolved in absolute ethyl alcohol, and the solution is heated to volatilize and is carried by inert carrier gas to be introduced into a deposition cavity of a microwave plasma chemical vapor deposition device.
4. The method for preparing the iron-doped diamond diluted magnetic semiconductor according to claim 2 or 3, wherein the concentration of the iron acetylacetonate in the absolute ethyl alcohol is 0.25-2.5 g/L.
5. The method for preparing an iron-doped diamond film according to claim 2 or 3, wherein the volatilization of the mixed solution of ferric acetylacetonate and absolute ethyl alcohol is accelerated by heating the mixed solution in a water bath at a temperature ranging from 35 ℃ to 50 ℃.
6. The method for preparing an iron-doped diamond diluted magnetic semiconductor according to claim 3, wherein the flow rate of the inert carrier gas is 5 to 10 sccm.
7. The method for producing an iron-doped diamond diluted magnetic semiconductor according to claim 1, wherein the substrate is previously subjected to ultrasonic cleaning using a diamond suspension.
8. The method for preparing the iron-doped diamond diluted magnetic semiconductor according to claim 1, which is characterized by mainly comprising the following steps of:
1) substrate pretreatment: the substrate is ultrasonically cleaned by using the diamond suspension, so that the surface energy of the substrate is increased, and diamond nucleation is facilitated;
2) preparing a precursor solution: dissolving ferric acetylacetonate into absolute ethyl alcohol in a conical flask to obtain a precursor solution, wherein the ferric acetylacetonate is used as an iron source, and the absolute ethyl alcohol is used as a carbon source;
3) preparing a device: putting a substrate into a deposition cavity of a microwave plasma chemical vapor deposition device, vacuumizing the cavity, introducing hydrogen into the cavity, adjusting microwave power and the air pressure in the vacuum cavity, and exciting to generate plasma, wherein the used process parameters are as follows: the hydrogen flow is 100-200 sccm, the microwave power is 700-1100W, the working pressure is 10-12 kPa, and the substrate temperature is 700-900 ℃;
4) heating the precursor solution in water bath at the temperature of 35-50 ℃ to increase the volatilization of the solution; and introducing carrier gas or not, wherein the carrier gas pipeline flows through the precursor solution when the carrier gas is introduced, so that the volatilization of the solution can be increased, the transmission of the ferric acetylacetonate is facilitated, and the used process parameters are as follows: the carrier gas flow is 0-10sccm, and the concentration of the ferric acetylacetonate in the absolute ethyl alcohol is 0.25-2.5 g/L;
5) adjusting a vacuum fine-tuning valve of the deposition cavity to keep the air pressure in the deposition cavity within a certain range and stabilize the state of the plasma, wherein the used process parameters are as follows: the air pressure in the cavity is 10-12 kPa, and the reaction time is 6-28h, so that the iron-doped diamond film, namely the iron-doped diamond diluted magnetic semiconductor, is obtained.
9. An iron-doped diamond diluted magnetic semiconductor prepared by the method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810786224.8A CN108914086B (en) | 2018-07-17 | 2018-07-17 | Iron-doped diamond diluted magnetic semiconductor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810786224.8A CN108914086B (en) | 2018-07-17 | 2018-07-17 | Iron-doped diamond diluted magnetic semiconductor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108914086A CN108914086A (en) | 2018-11-30 |
| CN108914086B true CN108914086B (en) | 2020-05-22 |
Family
ID=64414650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810786224.8A Active CN108914086B (en) | 2018-07-17 | 2018-07-17 | Iron-doped diamond diluted magnetic semiconductor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108914086B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114059159A (en) * | 2021-11-18 | 2022-02-18 | 北京大学东莞光电研究院 | Diamond growth method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020026495A (en) * | 2002-01-24 | 2002-04-10 | 조성래 | transition metal-doped ferromagnetic semiconductor single crystal |
| CN1810649A (en) * | 2006-02-23 | 2006-08-02 | 北京科技大学 | Low temperature process of preparing RE magnetic semiconductor of Mg-doped nanometer zine oxide line |
| CN1900356A (en) * | 2006-07-21 | 2007-01-24 | 上海大学 | Process for preparing diamond film under strong magnetic field |
| CN1996613A (en) * | 2000-08-22 | 2007-07-11 | 哈佛学院董事会 | Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices |
| CN101798057A (en) * | 2000-08-22 | 2010-08-11 | 哈佛学院董事会 | Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices |
-
2018
- 2018-07-17 CN CN201810786224.8A patent/CN108914086B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1996613A (en) * | 2000-08-22 | 2007-07-11 | 哈佛学院董事会 | Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices |
| CN101798057A (en) * | 2000-08-22 | 2010-08-11 | 哈佛学院董事会 | Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices |
| KR20020026495A (en) * | 2002-01-24 | 2002-04-10 | 조성래 | transition metal-doped ferromagnetic semiconductor single crystal |
| CN1810649A (en) * | 2006-02-23 | 2006-08-02 | 北京科技大学 | Low temperature process of preparing RE magnetic semiconductor of Mg-doped nanometer zine oxide line |
| CN1900356A (en) * | 2006-07-21 | 2007-01-24 | 上海大学 | Process for preparing diamond film under strong magnetic field |
Non-Patent Citations (1)
| Title |
|---|
| Magnetic properties of ion-implanted diamond;R. Höhne et al.;《Diamond & Related Materials》;20070127;第16卷(第8期);第1589-1596页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108914086A (en) | 2018-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107275192B (en) | High-performance diamond method for semiconductor is prepared based on inexpensive single-crystal diamond | |
| JP4427470B2 (en) | Method for producing silicon carbide single crystal | |
| CN106711022B (en) | A kind of preparation method of growth doped interface clearly silicon carbide epitaxial film | |
| CN111484019A (en) | Preparation method of high-purity silicon carbide powder for single crystal growth | |
| CN106011784B (en) | A method of preparing α phase molybdenum carbide crystal using microwave plasma CVD | |
| CN108914086B (en) | Iron-doped diamond diluted magnetic semiconductor and preparation method thereof | |
| CN105274624B (en) | A kind of method that utilization microwave irradiation prepares vanadium doping semi-insulating silicon carbide | |
| CN112647130A (en) | Method for growing gallium oxide film by low-pressure chemical vapor deposition | |
| JP2000031059A (en) | METHOD FOR SYNTHESIZING LOW RESISTANCE N-TYPE AND LOW RESISTANCE P-TYPE SINGLE CRYSTAL AlN THIN FILMS | |
| CN101174558A (en) | P type doping method for cubic boron nitride thin film | |
| CN109518159B (en) | Method for growing diamond by codoping transition metal elements and nitrogen | |
| CN105304498A (en) | Method for reducing SiO2/SiC interface state density | |
| CN104264219A (en) | Epitaxial preparation method for base region gradually doped silicon carbide film | |
| CN101859704B (en) | Preparation method of high-temperature and high-power field effect transistor | |
| TWI698397B (en) | Method of purifying silicon carbide powder | |
| CN101307485B (en) | Nitrogen source ionization method and device for semiconductor material vapor deposition growth system | |
| CN102154621A (en) | Method for preparing Ni-doped AlN-based diluted magnetic semiconductor thin-film material | |
| CN104131335A (en) | Doping source flow control N-type heavily-doped silicon carbide film epitaxial making method | |
| CN114334651A (en) | HEMT (high electron mobility transistor) preparation method based on ultrathin gallium nitride self-supporting substrate | |
| CN103334089B (en) | The preparation method of ECR-PEMOCVD low temperature depositing InN film on Diamond wafer | |
| CN103194798A (en) | Transition metal doped ZnO-based ferromagnetic polycrystalline thin film and preparation method thereof | |
| CN112820639A (en) | Improved preparation process of silicon carbide MOSFET device | |
| CN104233219A (en) | Method for preparing P-type heavily-doped silicon carbide thin film epitaxial layer by controlling doping source flow | |
| CN104233470A (en) | Method for preparing P-type lightly-doped silicon carbide thin film epitaxy by controlling hydrogen flow | |
| CN104233465A (en) | Preparation method for controlling epitaxial growth of heavily doped pressure N-type silicon carbide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231107 Address after: Room 101-201, Building 18, Donghu High tech Industrial Innovation Base, No. 9 Miaoshan Avenue, Jiangxia District, Wuhan City, Hubei Province, 430200 Patentee after: WUHAN PDVACUUM TECHNOLOGIES CO.,LTD. Address before: 430074, No. 693 Xiong Chu street, Hongshan District, Hubei, Wuhan Patentee before: WUHAN INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right |