CN116732485A - High-carrier mobility hydrogen-terminated diamond and preparation method thereof - Google Patents
High-carrier mobility hydrogen-terminated diamond and preparation method thereof Download PDFInfo
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- 239000010432 diamond Substances 0.000 title claims abstract description 168
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000001257 hydrogen Substances 0.000 claims abstract description 113
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 113
- 229910052582 BN Inorganic materials 0.000 claims abstract description 45
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000151 deposition Methods 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 238000001020 plasma etching Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000013077 target material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 241000252506 Characiformes Species 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000004047 hole gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
- C23C14/0647—Boron nitride
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
- C30B25/205—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer the substrate being of insulating material
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
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- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The application discloses a preparation method of a high-carrier mobility hydrogen-terminated diamond, which comprises the following steps: removing impurities on the surface of the diamond substrate, and then ultrasonically cleaning the surface of the diamond substrate; performing hydrogen plasma etching on the surface of the obtained diamond substrate to obtain diamond with the surface being a hydrogen terminal; and taking hexagonal boron nitride as a target material, and performing magnetron sputtering deposition on the hydrogen terminal surface of the diamond to obtain the high-carrier mobility hydrogen terminal diamond with the surface containing boron nitride. The preparation method is simple and efficient. The application also discloses the high-carrier mobility hydrogen-terminated diamond prepared by the preparation method of the high-carrier mobility hydrogen-terminated diamond, and the boron nitride-deposited hydrogen-terminated diamond has higher carrier mobility and carrier mobility stability.
Description
Technical Field
The application belongs to the technical field of semiconductor device preparation, and particularly relates to a high-carrier mobility hydrogen termination diamond and a preparation method thereof.
Background
With the rapid development of aerospace, mobile communication and automobile fields in recent years, a power semiconductor device gradually advances to the extreme application directions of high power, high frequency, high speed, high temperature, high pressure and the like. The most mature silicon material used at present has a narrow band gap (1.12 eV), a small breakdown electric field (0.3 MV/cm) and relatively low thermal conductivity (1.5W/cm.K), and therefore the silicon material has a plurality of limitations in the application of high-frequency high-power devices.
Subsequently, the wide bandgap semiconductor materials represented by GaN and SiC show wide application prospects in high-temperature high-frequency high-power devices by virtue of excellent characteristics such as wide bandgap, large breakdown electric field and the like, however, the GaN has the defect of poor heat dissipation as a high-frequency device due to low thermal conductivity (1.3W/cm & K), and the SiC is mainly concentrated in power device application.
Thus based on ultra-wide band gap semiconductor material (band gap Eg>3.4 eV) has become an international leading-edge hotspot in device research and industrialization. Among the numerous ultra-wide band gap semiconductor materials, diamond has, for example, a wide band gap (5.47 eV), high thermal conductivity (22W/cm. K), high breakdown field (10 MV/cm), and high carrier mobility (electrons: 4500 cm) 2 V.s; a hole: 3800cm 2 Excellent physical properties such as/v·s) and low dielectric constant (5.7) make it extremely important to apply potential in the field of high temperature, high frequency, high power electronics, also referred to as "final semiconductor material".
However, the boron and phosphorus dopants commonly used in current p-type and n-type diamond body doping often have large impurity ionization energies, namely 0.37eV and 0.57eV, respectively, and tend to cause incomplete ionization at room temperature, which severely hinders the application and development of diamond in the field of electronic devices.
However, dangling bonds of the surface C atoms of the diamond after the hydrogen plasma treatment form C-H bonds, namely hydrogen terminals, and when the diamond with the hydrogen terminals is exposed to air for a period of time, a layer of two-dimensional hole gas (two-dimensional hole gas,2 DHG) is formed on the surface, and the diamond has the characteristic of p-type conductivity. At room temperature, the conductivity of 2DHG is 10 -4 ～10 -5 S-level, carrier concentration of 10 12 –10 14 cm -2 Mobility of 50-200cm 2 V -1 s -1 Between them. The discovery of the conductivity of the surface of the hydrogen-terminated diamond provides a new idea for the application of diamond in the field of electronic devices. However, the carrier mobility of the 2DHG of the current hydrogen-terminated diamond is generally low, and the current hydrogen-terminated diamond is greatly influenced by environmental factors, so that the application of the hydrogen-terminated diamond to electronic devices is greatly limited. How to improve the carrier mobility of hydrogen terminated diamond 2DHG, as well as achieving reliable stability and repeatability thereof, is therefore currently the most desirable issue to be addressed and resolved.
Aiming at the defects of the hydrogen terminal diamond, the solution adopted at present is to deposit a dielectric layer on the surface of the diamond, passivate the surface of a C-H bond, and the metal oxide is a common solid packaging material for improving the conductivity stability of the surface of the hydrogen terminal. However, the metal oxide, particularly the transition metal oxide, has higher electron affinity, and can induce the surface transfer doping of the hydrogen-terminated diamond, so that the carrier concentration of the surface of the hydrogen-terminated diamond is obviously improved, and the surface mobility of the hydrogen-terminated diamond is reduced.
Disclosure of Invention
The application provides a preparation method of a hydrogen-terminated diamond with high carrier mobility, which is simple and efficient, and the prepared hydrogen-terminated diamond has higher carrier mobility and carrier mobility stability.
The embodiment of the application provides a preparation method of a high-carrier mobility hydrogen-terminated diamond, which comprises the following steps:
(1) Removing impurities on the surface of the diamond substrate, and then ultrasonically cleaning the surface of the diamond substrate;
(2) Performing hydrogen plasma etching on the surface of the diamond substrate obtained in the step (1) to obtain diamond with the surface being a hydrogen terminal;
(3) And taking hexagonal boron nitride as a target material, and performing magnetron sputtering deposition on the hydrogen terminal surface of the diamond to obtain the hydrogen terminal diamond with the surface containing boron nitride.
The application discloses a method for directly depositing hexagonal boron nitride on the surface of diamond with a hydrogen terminal on the surface by a magnetron sputtering method for the first time to obtain the hydrogen terminal diamond with the surface containing boron nitride, and the obtained hydrogen terminal diamond with the surface containing boron nitride has higher carrier mobility and higher carrier mobility stability.
Further, the hydrogen terminal diamond with boron nitride on the surface is obtained by performing magnetron sputtering deposition on the hydrogen terminal surface of the diamond, and the technological parameters of the magnetron sputtering deposition are as follows: the deposition pressure is 0.5-5Pa, the power is 80-300W, and the deposition time is 5s-60min. Can obtain 600-1200cm under reasonable technological parameters 2 V -1 s -1 And carrier mobility remains stable for 20-60 days.
Further, the removing of the impurities on the surface of the diamond comprises the following steps: and immersing the diamond in the piranha cleaning solution to remove impurities on the surface of the diamond.
Further, the ultrasonic cleaning of the diamond surface comprises: and sequentially carrying out ultrasonic cleaning on the surface of the diamond through deionized water, acetone and absolute ethyl alcohol. Thereby cleaning the diamond surface.
Further, the preparation method of the high carrier mobility hydrogen termination diamond further comprises the following steps:
and (3) epitaxially growing a diamond epitaxial layer on the surface of the diamond obtained in the step (1), and performing hydrogen plasma etching on the diamond epitaxial layer to obtain the diamond with the surface being a hydrogen terminal. By growing a diamond epitaxial layer with high quality and low defects, scratches and defects on the surface of the cleaned diamond are covered, so that the formed hydrogen terminal has higher carrier mobility, and a good foundation is laid for obtaining a hydrogen terminal diamond field with higher carrier mobility.
Further preferably, a layer of diamond epitaxial layer is epitaxially grown on the diamond surface obtained in the step (1), and the technological parameters of epitaxial growth are as follows: the hydrogen flow is 300-600sccm, the methane flow is 1% -5% of the hydrogen flow, the pressure is 10-18kPa, the power is 3.0-5.0kW, and the growth temperature is 800-1200 ℃.
Further, performing hydrogen plasma etching on the surface of the diamond obtained in the step (1) to obtain a diamond with a hydrogen terminal surface, wherein the technological parameters of the hydrogen plasma etching are as follows: the hydrogen flow is 300-600sccm, the pressure is 8-15kPa, the power is 2.0-4.0kW, the etching temperature is 600-900 ℃, and the etching time is 5-60min.
The application also provides the high-carrier-mobility hydrogen-terminated diamond, which is prepared by the preparation method of the high-carrier-mobility hydrogen-terminated diamond.
Further, the boron nitride deposited on the hydrogen-terminated diamond is single crystal, polycrystalline, amorphous or nanocluster particles, wherein the atomic ratio of boron to nitrogen is 0.1-10.
Further, the diamond in the hydrogen termination diamond substrate is monocrystalline diamond or polycrystalline diamond.
Further, the preparation method of the diamond comprises chemical vapor deposition or a high-temperature high-pressure method.
Further, the carrier mobility of the surface of the hydrogen-terminated diamond is 600-1200cm 2 V -1 s -1 The hydrogen terminated diamond deposited with boron nitride was exposed to air for 60 days with a carrier mobility change rate of ±5%.
Compared with the prior art, the application has the beneficial effects that:
the application provides a method for controlling the diamond surface on the hydrogen terminal by magnetism for the first timeThe sputtering technology directly deposits boron nitride, the obtained hydrogen terminal diamond with the surface containing boron nitride realizes the improvement of the electrical property (carrier mobility) of the surface of the original hydrogen terminal diamond, the preparation method is simple and efficient, and the carrier mobility of the prepared hydrogen terminal diamond deposited with boron nitride is 600-1200cm 2 V -1 s -1 The rate of change of carrier mobility of the hydrogen terminated diamond deposited with boron nitride was-5% within 60 days.
Drawings
FIG. 1 is a top view of a high carrier mobility hydrogen terminated diamond according to an embodiment of the present application;
FIG. 2 is a cross-sectional view of a high carrier mobility hydrogen terminated diamond according to an embodiment of the present application;
FIG. 3 is a graph showing changes in carrier mobility of the hydrogen terminated diamond of comparative example 1, the boron nitride deposited hydrogen terminated diamond of example 1, and the boron nitride deposited hydrogen terminated diamond of example 1 exposed to air for 42 days and 60 days;
fig. 4 is a graph showing changes in carrier mobility of the hydrogen terminated diamond prepared in comparative example 1, the boron nitride deposited hydrogen terminated diamond prepared in example 2, and the boron nitride deposited hydrogen terminated diamond prepared in example 2 exposed to air for 42 days and 60 days.
FIG. 5 is a graph showing changes in carrier mobility of the hydrogen terminated diamond of comparative example 1, the boron nitride deposited hydrogen terminated diamond of example 3, and the boron nitride deposited hydrogen terminated diamond of example 3 exposed to air for 42 days and 60 days;
fig. 6 is an XPS diagram of BN deposited with boron nitride hydrogen terminated diamond prepared in example 1.
Wherein, a diamond substrate 1, a hydrogen terminal 2 and boron nitride 3.
Detailed Description
The application is described in detail below in connection with the drawings and the specific embodiments, but these examples are not intended to limit the scope of the application in any way.
In order to solve the technical problems of lower carrier mobility and poor stability in the prior art, the embodiment of the application provides a scheme for improving carrier mobility and stability of the surface of a hydrogen terminal diamond, and as shown in fig. 1 and 2, the hydrogen terminal diamond structure comprises a diamond substrate 1, a hydrogen terminal 2 and boron nitride 3, wherein the surface of the diamond substrate 1 is provided with the hydrogen terminal 2, and the boron nitride 3 is deposited on the surface of the hydrogen terminal 2 by magnetron sputtering. The obtained hydrogen termination diamond deposited with boron nitride has higher carrier mobility and carrier mobility stability.
Example 1
The embodiment provides a preparation method of a high-carrier mobility hydrogen-terminated diamond, which comprises the following steps:
(1) Cleaning the monocrystalline diamond for 8 hours by using standard piranha liquid to remove organic matters on the surface; ultrasonic cleaning is carried out for 10 minutes by using deionized water, acetone and absolute ethyl alcohol respectively, and nitrogen purging is carried out for 3 seconds to obtain the diamond substrate 1.
(2) Performing hydrogen plasma etching on the diamond substrate 1 to obtain diamond with the surface containing the hydrogen terminal 2; the technological parameters of hydrogen plasma etching are as follows: controlling the hydrogen flow rate to 400sccm, the pressure to 10kPa, the microwave power to 3000W, the temperature to 850 ℃ and the etching time to 10min.
(3) And placing the diamond containing the hydrogen terminal into a reaction chamber of magnetron sputtering to deposit a layer of boron nitride nano particles, wherein the deposition pressure is 1.0Pa, the power is 120W, the deposition time is 3 minutes, the diameter of the deposited nano particles is 10-20nm, and the nitrogen-boron ratio of the deposited boron nitride nano particles is 7.29:35.91 as shown in figure 6.
Example 2
The embodiment provides a preparation method of a high-carrier mobility hydrogen-terminated diamond, which comprises the following steps:
(1) Cleaning the monocrystalline diamond for 8 hours by using standard piranha liquid to remove organic matters on the surface; ultrasonic cleaning is carried out for 10 minutes by using deionized water, acetone and absolute ethyl alcohol respectively, and nitrogen purging is carried out for 3 seconds to obtain the diamond substrate 1.
(2) Carrying out epitaxial growth on the diamond substrate 1 to obtain diamond with the surface containing the hydrogen terminal 2; the technological parameters of epitaxial growth are as follows: controlling the hydrogen flow rate to 400sccm, the methane flow rate to 12sccm, the pressure to 16kPa, the microwave power to 4200W, the temperature to 960 ℃ and the growth time to 2 hours.
(3) And placing the diamond containing the hydrogen terminal into a reaction chamber of magnetron sputtering to deposit a layer of boron nitride film 3, wherein the deposition pressure is 1.0Pa, the power is 150W, the deposition time is 1min, and the diameter of deposited BN particles is 5-10nm.
Example 3
The embodiment provides a preparation method of a high-carrier mobility hydrogen-terminated diamond, which comprises the following steps:
(1) Cleaning the monocrystalline diamond for 8 hours by using standard piranha liquid to remove organic matters on the surface; ultrasonic cleaning is carried out for 10 minutes by using deionized water, acetone and absolute ethyl alcohol respectively, and nitrogen purging is carried out for 3 seconds to obtain the diamond substrate 1.
(2) Carrying out epitaxial growth on the diamond substrate 1 to obtain diamond with the surface containing the hydrogen terminal 2; the technological parameters of epitaxial growth are as follows: controlling the hydrogen flow rate to 400sccm, the methane flow rate to 12sccm, the pressure to 16kPa, the microwave power to 4200W, the temperature to 960 ℃ and the growth time to 2 hours.
(3) Continuously carrying out hydrogen plasma treatment on the grown diamond substrate 1 to obtain a surface hydrogen terminal 2; after closing methane, keeping the hydrogen flow at 400sccm, reducing the pressure to 10kPa, reducing the power to 3000W, and treating for 15min at 830-850 ℃;
(4) And placing the diamond containing the hydrogen terminal into a reaction chamber of magnetron sputtering to deposit a layer of boron nitride film 3, wherein the deposition pressure is 1.0Pa, the power is 150W, the deposition time is 30s, and the diameter of deposited BN particles is 3-5nm.
Comparative example 1
The present comparative example provides a method of preparing hydrogen terminated diamond comprising:
(1) Cleaning the monocrystalline diamond for 8 hours by using standard piranha liquid to remove organic matters on the surface; ultrasonic cleaning is carried out for 10 minutes by using deionized water, acetone and absolute ethyl alcohol respectively, and nitrogen purging is carried out for 3 seconds to obtain the diamond substrate 1.
(2) Carrying out epitaxial growth on the diamond substrate 1 to obtain diamond with the surface containing the hydrogen terminal 2; the technological parameters of epitaxial growth are as follows: controlling the hydrogen flow rate to 400sccm, the methane flow rate to 12sccm, the pressure to 16kPa, the microwave power to 4200W, the temperature to 960 ℃ and the growth time to 2 hours.
Comparative example 2
The present comparative example provides a method of preparing hydrogen terminated diamond comprising:
(1) Cleaning the monocrystalline diamond for 8 hours by using standard piranha liquid to remove organic matters on the surface; ultrasonic cleaning is carried out for 10 minutes by using deionized water, acetone and absolute ethyl alcohol respectively, and nitrogen purging is carried out for 3 seconds to obtain the diamond substrate 1.
(2) Carrying out epitaxial growth on the diamond substrate 1 to obtain diamond with the surface containing the hydrogen terminal 2; the technological parameters of epitaxial growth are as follows: controlling the hydrogen flow rate to 400sccm, the methane flow rate to 12sccm, the pressure to 16kPa, the microwave power to 4200W, the temperature to 960 ℃ and the growth time to 2 hours.
(3) And placing the diamond containing the hydrogen terminal into a reaction chamber of magnetron sputtering to deposit a layer of boron nitride film 3, wherein the deposition pressure is 1.0Pa, the power is 150W, the deposition time is 90min, and the deposition BN is used for forming a film with the thickness of about 150nm.
Performance analysis
As shown in fig. 3, for example 1, comparative example 1 was measured for carrier mobility of hydrogen terminated diamond surface before and after boron nitride deposition, and after 42 days and 60 days of exposure to air after deposition, respectively. The carrier mobility of the hydrogen terminated diamond after boron nitride deposition obtained in example 1 was improved by 11 (620 cm 2 V -1 s -1 ) About twice as much as the above, and can be kept stable for a long time.
As shown in fig. 4, for example 2, comparative example 1 measured carrier mobility of hydrogen terminated diamond surface before and after boron nitride deposition, and after 42 days and 60 days of exposure to air after deposition, respectively. The carrier mobility of the hydrogen terminated diamond after boron nitride deposition obtained in example 2 was improved by 10 (1100 cm) compared to the original hydrogen terminated diamond obtained in comparative example 1 2 V -1 s -1 ) About twice as much as the above, and can be kept stable for a long time.
As shown in fig. 5, for example 3, comparative example 1 measured carrier mobility of hydrogen terminated diamond surface before and after boron nitride deposition, and after 42 days and 60 days of exposure to air after deposition, respectively. The carrier mobility of the hydrogen terminated diamond after boron nitride deposition obtained in example 3 was improved by 7 (940 cm) compared to the original hydrogen terminated diamond obtained in comparative example 1 2 V -1 s -1 ) About twice as much as the above, and can be kept stable for a long time.
For comparative example 2, the carrier mobility of the hydrogen terminated diamond surface was measured before and after boron nitride deposition, and after 42 days and 60 days of exposure to air after deposition, respectively. The boron nitride deposited hydrogen terminated diamond surface of comparative example 2 exhibited a high electrical resistance (10 12 Ω) in which case the carrier mobility cannot be measured.
The foregoing examples are illustrative of the present application and are not intended to be limiting, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the application will be made by the foregoing examples, and many other non-essential modifications and variations will be apparent to those skilled in the art from the foregoing description of the application. The specific device parameters, times, etc. described below are also but one example of suitable ranges, i.e., one skilled in the art can make appropriate selections from the description herein, and are not intended to be limited to the specific values described below. So that equivalents and modifications will fall within the scope of the application, all within the spirit and scope of the application as disclosed.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (10)
1. A method for preparing a high carrier mobility hydrogen terminated diamond, comprising:
(1) Removing impurities on the surface of the diamond substrate, and then ultrasonically cleaning the surface of the diamond substrate;
(2) Performing hydrogen plasma etching on the surface of the diamond substrate obtained in the step (1) to obtain diamond with the surface being a hydrogen terminal;
(3) And taking hexagonal boron nitride as a target material, and performing magnetron sputtering deposition on the hydrogen terminal surface of the diamond to obtain the high-carrier mobility hydrogen terminal diamond with the surface containing boron nitride.
2. The method for preparing the high-carrier mobility hydrogen-terminated diamond according to claim 1, wherein the magnetron sputtering deposition is performed on the hydrogen-terminated surface of the diamond to obtain the hydrogen-terminated diamond with boron nitride on the surface, and the technological parameters of the magnetron sputtering deposition are as follows: the deposition pressure is 0.5-5Pa, the power is 80-300W, and the deposition time is 5s-60min.
3. The method for preparing a high carrier mobility hydrogen terminated diamond according to claim 1, wherein the removing of the impurities on the diamond surface comprises: and immersing the diamond in the piranha cleaning solution to remove impurities on the surface of the diamond.
4. The method for preparing a high carrier mobility hydrogen terminated diamond according to claim 1, wherein the ultrasonic cleaning of the diamond surface comprises: and sequentially carrying out ultrasonic cleaning on the surface of the diamond through deionized water, acetone and absolute ethyl alcohol.
5. The method of preparing a high carrier mobility hydrogen terminated diamond according to claim 1, further comprising:
and (3) epitaxially growing a diamond epitaxial layer on the surface of the diamond obtained in the step (1), and performing hydrogen plasma etching on the diamond epitaxial layer to obtain the diamond with the surface being a hydrogen terminal.
6. The method for preparing a high carrier mobility hydrogen terminated diamond according to claim 5, wherein the process parameters of epitaxial growth are: the hydrogen flow is 300-600sccm, the methane flow is 1% -5% of the hydrogen flow, the pressure is 10-18kPa, the power is 3.0-5.0kW, and the growth temperature is 800-1200 ℃.
7. The method for preparing the high carrier mobility hydrogen terminated diamond according to claim 1, wherein the diamond surface obtained in the step (1) is subjected to hydrogen plasma etching to obtain the diamond with the surface being a hydrogen termination, and the technological parameters of the hydrogen plasma etching are as follows: the hydrogen flow is 300-600sccm, the pressure is 8-15kPa, the power is 2.0-4.0kW, the etching temperature is 600-900 ℃, and the etching time is 5-60min.
8. A high carrier mobility hydrogen terminated diamond prepared by a method according to any one of claims 1 to 7.
9. The high carrier mobility hydrogen terminated diamond of claim 8, wherein the boron nitride deposited on the surface of the hydrogen terminated diamond is single crystal, polycrystalline, amorphous, or nanocluster particles, wherein the ratio of boron to nitrogen atoms is 0.1 to 10.
10. The high carrier mobility hydrogen terminated diamond of claim 8, wherein the boron nitride deposited hydrogen terminated diamond has a surface carrier mobility of 600 cm to 1200cm 2 V -1 s -1 Exposing the hydrogen terminated diamond deposited with boron nitride to air for 20-60 days, wherein the change rate of carrier mobility of the hydrogen terminated diamond deposited with boron nitride is-5%.
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