CN115161767A - Preparation method of (100)/(111) oriented composite high-performance diamond semiconductor - Google Patents
Preparation method of (100)/(111) oriented composite high-performance diamond semiconductor Download PDFInfo
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- C30B28/00—Production of homogeneous polycrystalline material with defined structure
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Abstract
A preparation method of a (100)/(111) oriented composite high-performance diamond semiconductor belongs to the field of diamond semiconductor materials. The process comprises the following steps: a. screening dislocation density greater than 10 6 /cm 2 The (100) diamond seed of (1); b. exposing dislocation by using plasma etching; c. the formation of high-density polycrystalline points is realized through the control of a growth process; d. fine polishing the surface to form a diamond material with a composite of (100) and (111) orientations; e. by means of doped epitaxial growth or hydrogenation treatment, differential conduction of (100) and (111) orientations is achieved, and a diamond semiconductor with comprehensively improved carrier mobility and carrier density is formed. The invention utilizes the dislocation defect of the (100) single crystal diamond substrate and regulates and controls the growth process of the microwave plasma chemical vapor deposition technology, so that the nucleation grows to have (111) selectivityThe oriented polycrystalline diamond is optimized, so that the diamond material compounded by (100) orientation and (111) orientation is formed, the requirements on materials and processes are simple, and the process universality is realized.
Description
Technical Field
The invention belongs to the technical field of diamond semiconductor material growth, and specifically comprises the following steps: when the single crystal diamond grows, firstly, dislocation defects of a single crystal diamond substrate are used as dominant positions, and a growth process of a microwave plasma chemical vapor deposition technology is regulated, so that nucleation grows into polycrystalline diamond with preferred orientation, and finally, the diamond semiconductor material compounded with (100) and (111) orientations is formed through epitaxial doping or surface hydrogenation treatment.
Technical Field
Diamond is widely used in various fields due to its excellent properties of high hardness, rapid thermal conductivity, high breakdown electric field threshold, and the like. In recent years, researchers have made efforts to study the electrical conductivity of diamond as a new generation of ultra-wide bandgap semiconductor (the bandgap width is 5.6 eV). The electron mobility of intrinsic diamond is 4500cm 2 V -1 s -1 Hole mobility of 3800cm 2 V -1 s -1 Current research on diamond semiconductors is largely divided into doping to form P-type or N-type semiconductors, and forming P-type conducting hydrogen-terminated diamonds. For p-type doped diamond materials, researchers have mainly passedB doping, although research shows that the hole mobility can reach 3000cm 2 V -1 s -1 The above, such as Yamanaka, uses microwave plasma Chemical Vapor Deposition (CVD) technique to remove B (CH) from trimethylboron 3 ) 3 The gas is a boron doping source, and the Hall mobility can reach 3370cm at 170K 2 V -1 s -1 (Phys Status Solidi,1999,1, 59.), but the increase in mobility is accompanied by a decrease in carrier concentration, making the effective activation carrier concentration lower. The hole mobility of hydrogen-terminated diamond is mostly tens to three hundred cm higher than that of a material with a higher hall mobility formed by B doping 2 V -1 s -1 In between. For N-type doping, researchers at home and abroad research the doping of elements such as sodium, nitrogen, phosphorus, sulfur and the like, but the results are not ideal. Poor conductivity of diamond semiconductor prepared by doping diamond element and hydrogen terminal technology is closely related to the orientation of the substrate. Generally, (100) oriented diamond has few intrinsic defects, but impurity doping with high concentration is difficult to realize, and for (110) orientation and (111) orientation, although impurity elements are easy to dope, the defect density is high, so that the comprehensive performance is not good. Also for hydrogen terminated diamonds, while high quality diamond material is produced with a (100) orientation, the hydrogen terminated diamond (100) orientation has a significantly lower plane carrier concentration than the (110) and (111) orientations. These problems with diamond semiconductors, caused by orientation, have greatly limited their development in electronic devices.
Disclosure of Invention
In order to solve the problems, the invention provides a high-performance diamond semiconductor which preferentially grows (111) oriented polycrystal on (100) crystal face diamond by utilizing a seed crystal dislocation defect position, thereby realizing a composite material of (100) monocrystal and (111) polycrystal, realizes different concentration doping by utilizing the impurity doping efficiency difference, obtains the composite enhancement effect of mobility and concentration, and finally realizes high mobility and high carrier density.
A preparation method of a (100)/(111) oriented composite high-performance diamond semiconductor comprises the following specific implementation steps:
step 1: screening of seed crystals
Screening dislocation density greater than 10 6 /cm 2 The diamond (100) oriented seed of (a);
step 2: outcrop of dislocation
And precisely polishing the screened seed crystals by using a polishing machine to obtain the surface roughness beneficial to epitaxial growth. And removing substances such as surface impurities and the like by acid washing and ultrasonic treatment. And then carrying out plasma etching by using microwave plasma chemical vapor deposition equipment to expose dislocations.
And step 3: (111) Growth of oriented high density polycrystalline dots
The growth process is adjusted by a microwave plasma chemical vapor deposition technology, homoepitaxial growth is carried out, and the formation of high-density (111) oriented polycrystalline points is realized.
And 4, step 4: (100) Formation of single crystal and (111) polycrystalline composites
And (3) grinding and polishing the sample in the step (3) to obtain a (100) monocrystal and (111) polycrystal composite material, and then carrying out acid washing and ultrasonic treatment for epitaxial growth and surface hydrogenation treatment.
And 5: formation of doped or hydrogen terminated diamonds
And (3) carrying out epitaxial impurity doping growth on the single crystal and polycrystalline composite materials processed in the step (4) by using a microwave plasma chemical vapor deposition technology to form doped diamond, or forming hydrogen terminal diamond by using a microwave plasma hydrogenation mode. The epitaxial impurity doping is divided into P-type conduction and N-type conduction.
Further, the seed selection in step 1 is from 3mm X3 mm to 10mm X10 mm, the seed selection may be CVD or HTHP, and the crystal average dislocation density may be calculated using X-ray diffraction peak Full Width Half Maximum (FWHM) fitting.
Further, the precise polishing parameters in step 2 are: polishing for 5-10min until RMS value less than 1nm is reached.
Further, the specific steps of acid washing and ultrasound in the step 2 are as follows: adopts 200-250 ℃ of HNO 3 /H 2 SO 4 =1:3-5 for 20-40min to remove surface goldBelonging to impurities such as particles, organic matters and the like, respectively performing ultrasonic treatment for 5-10min by using acetone and alcohol, and then drying in a nitrogen atmosphere.
Further, the specific step of enabling the dislocation to be exposed in the step 2 is as follows: putting the treated seed crystal into microwave chemical vapor deposition equipment, and introducing H 2 /O 2 And carrying out plasma etching, wherein the etching temperature is 600-800 ℃, and the etching lasts for at least more than 1h, so that the dislocation is exposed.
Further, the specific steps of the polycrystalline point growth in the step 3 are as follows: and (2) carrying out homoepitaxial growth of the diamond by adopting a microwave plasma chemical vapor deposition system (MPCVD), putting the treated seed crystal on a deposition table of MPCVD equipment, and carrying out diamond growth at the temperature of more than or equal to 900 ℃ and the methane concentration of more than 5 percent to realize (111) oriented polycrystalline points with different densities.
Further, the grinding and polishing steps in step 4 are as follows: diamond powder with the grain size from large to small is selected according to the above, and is ground for 1-1.5 hours each time for 10 minutes until the surface is relatively flat. And then performing precision polishing, performing powder pressing treatment on the polishing machine before polishing, wherein the polishing time is 20min each time, polishing for 1-1.5h, and polishing until the RMS value of the crystal surface except the polycrystalline point reaches less than 1nm.
Further, the acid washing and ultrasonic treatment in step 4 are the same as those in step 2 (i.e. adopting 200-250 ℃ and HNO) 3 /H 2 SO 4 =1:3-5 of acid mixed solution for 20-40min, respectively carrying out ultrasonic treatment on the surface of the metal particles, organic matters and other impurities for 5-10min by using acetone and alcohol, and then drying the mixture in the nitrogen atmosphere. )
Further, the epitaxial doping in step 5 to form the P-type conductivity specifically comprises the following steps: taking B doping as an example, putting the treated product in the step 4 into Microwave Plasma Chemical Vapor Deposition (MPCVD) equipment, wherein a carbon source gas is methane, and simultaneously doping a gas required by epitaxial growth of an element B, wherein the growth temperature is 900-1200 ℃, the methane flow accounts for 0.1-5%, the B/C ratio is 50-50000ppm, and the growth time is more than or equal to 1h.
Further, the specific steps of forming the N-type conductivity by epitaxial doping in the step 5 are as follows: taking P doping as an example, putting the treated product in the step 4 into Microwave Plasma Chemical Vapor Deposition (MPCVD) equipment, wherein a carbon source gas is methane, and simultaneously doping a gas required by epitaxial growth of a P element, wherein the growth temperature is 900-1200 ℃, the flow rate of the methane accounts for 0.1-5%, the ratio of P to C is 50-50000ppm, and the growth time is more than or equal to 1h.
Further, the specific steps of the surface hydrogenation treatment in step 5 are as follows: putting the steps into an MPCVD device, adopting a microwave plasma hydrogenation mode, controlling the temperature range to be 650-750 ℃, controlling the processing time to be 8-15min, and keeping the introduction of hydrogen to the room temperature when the plasma power supply is closed again in order to avoid the influence of other gases.
The key of the implementation process of the invention is as follows:
(1) To ensure high density (111) oriented polycrystalline production, the dislocation density of the screened (100) diamond seed must be greater than 10 6 /cm 2 Thereby realizing the formation of the (100) single crystal and (111) polycrystalline composite material by utilizing the dislocation dominant position.
(2) Polishing treatment is needed before epitaxial growth, and in order to simultaneously meet the requirements of (100) oriented epitaxial growth and (111) oriented diamond controllable growth, the surface of a sample needs to be flat enough, and the surface roughness of diamond is required to be less than 1nm.
(3) In order to realize the (111) polycrystalline orientation distribution in a controllable way, the dislocation on the surface of the diamond needs to be exposed, meanwhile, the dislocation proliferation caused by surface processing is etched, the temperature is not high enough, otherwise, the surface roughness is too large, the (100) orientation epitaxial growth is not facilitated, and the surface dislocation cannot be sufficiently exposed due to too low temperature.
(4) For (100) oriented single crystal diamond growth (111) oriented polycrystalline diamond, the deposition temperature and methane must not be too low, otherwise polycrystallization cannot be achieved, typically temperatures greater than 900 ℃ and methane concentrations greater than 5%. Too high a deposition temperature and methane at the same time can cause the surface to rapidly form (111) oriented cores, so that the (100) oriented diamond is covered.
(5) For the preparation of the (100)/(111) oriented composite diamond material, a surface finish is required in preparation for further epitaxial growth of the doped diamond or surface hydrogenation treatment.
(6) The process for realizing the diamond semiconductor can form a doped type P-type diamond semiconductor by doping boron and the like; a doped N-type diamond semiconductor may also be formed by doping phosphorus element or the like; or by surface hydrogenation treatment to form a P-type hydrogen-terminated diamond semiconductor.
(7) For epitaxial P-type doping growth of the (100)/(111) oriented composite diamond material, the doping temperature is higher than the growth temperature, the proper reduction of the methane proportion is beneficial to differential doping, the too high methane proportion is not suitable for doping, the doping range comprises light doping to heavy doping, the heavy doping range avoids forming superconduction, and the doping time is properly prolonged due to the existence of polycrystal and monocrystal at the same time.
(8) For the epitaxial N-type doping growth of the (100)/(111) oriented composite diamond material, the doping temperature is higher than the growth temperature, the proper reduction of the methane proportion is favorable for differential doping, the too high methane proportion is not suitable for doping, the doping range is from light doping to heavy doping, and the doping time is properly prolonged due to the existence of both polycrystal and monocrystal.
(9) Hydrogen termination is preferably achieved on the surface of the (100)/(111) oriented composite diamond material to form hydrogen termination on the surface without causing significant etching of the surface. The surface temperature of the diamond is 650-750 ℃ usually, and the treatment time is 8-15min.
The invention and the prior art have the beneficial effects that:
(1) The (111) oriented diamond grows by taking the single crystal diamond dislocation defect as a template, the template effect of the composite material by utilizing the diamond dislocation defect is realized, and the (111) preferred oriented diamond growth process is relatively simple.
(2) The diamond semiconductor compounded by (100) and (111) obtained by the invention can solve the problem that the mobility of a single orientation doping carrier and the concentration of the carrier are mutually restricted, and the high-performance diamond semiconductor is obtained.
(3) The invention can grow on the single crystal diamond substrate with dislocation defects, does not need high-quality single crystal diamond, has simple requirements on materials and processes, and has process universality.
Drawings
In order to more clearly explain the technical solution of the present invention, the drawings used in the embodiments will be briefly described below. The following drawings are merely schematic representations of the present invention.
FIG. 1 is a process flow chart of the preparation method of the (100)/(111) oriented composite high-performance diamond semiconductor.
Detailed Description
The technical solution in the embodiment of the present invention is clearly and completely described below with reference to the drawings in the embodiment of the present invention.
Example 1
The dislocation density of 2.0 x 10 will be screened 6 /cm 2 Diamond (100) CVD seed crystals with the size of 4mm multiplied by 0.5mm are precisely polished by a polishing machine, the polishing machine needs to carry out powder pressing treatment before polishing, each time of polishing is 20min, and the polishing time is more than 40min until the RMS value reaches 0.80nm. Placing the seed crystal at 200 deg.C H 2 SO 4 ＝25ml，HNO 3 Washing with 5ml acidic mixed solution for 20min, and ultrasonic treating with acetone and ethanol for 5min. Putting the seed crystal on a deposition table of MPCVD equipment, closing a deposition cavity, vacuumizing the cavity, and introducing H 2 /O 2 And carrying out plasma etching, setting the temperature to be 750 ℃, and etching for 1h to enable dislocation to be exposed. Carrying out homoepitaxial growth on the diamond by adopting a microwave plasma chemical vapor deposition system (MPCVD), putting the treated seed crystal on a deposition table of MPCVD equipment, closing a deposition chamber, vacuumizing the chamber, introducing 300sccm of hydrogen, setting the temperature to 900 ℃, introducing 20sccm of methane gas and 1.2sccm of oxygen after the temperature reaches the set temperature, and carrying out diamond growth for 72 hours to obtain a (100) oriented single crystal and a (111) oriented polycrystalline composite diamond; and then, selecting 40W and 20W diamond powder to grind the diamond for 1h until the surface is relatively flat, and performing powder pressing treatment on a polishing machine for 20min each time until the roughness of the crystal surface except the polycrystalline point is 0.50nm. Again using 200 ℃ H 2 SO 4 ＝25ml，HNO 3 =5ml of acidCleaning with mixed solution for 20min, and respectively ultrasonic treating with acetone and alcohol for 5min; putting the treated sample into Microwave Plasma Chemical Vapor Deposition (MPCVD) equipment, closing a deposition cavity, vacuumizing the cavity, introducing hydrogen, wherein a carbon source gas is methane, a boron source gas is trimethyl borate, the set temperature is 950 ℃, the methane flow rate is 1%, the B/C ratio is 1000ppm, the growth time is 3h, and finally, the resistivity is measured to be 253m omega cm.
Example 2
The dislocation density of 1.5X 10 will be screened 6 /cm 2 And diamond (100) CVD seed crystal with the size of 4mm multiplied by 0.5mm is precisely polished by a polishing machine, the polishing machine needs to carry out powder pressing treatment before polishing, each polishing time is 20min, and the polishing time is more than 40min until the RMS value reaches 0.55nm. Placing the seed crystal at 200 deg.C H 2 SO 4 ＝25ml，HNO 3 Washing with 5ml acidic mixed solution for 20min, and ultrasonic treating with acetone and ethanol for 5min. Putting the seed crystal on a deposition table of MPCVD equipment, closing a deposition cavity, vacuumizing the cavity, and introducing H 2 /O 2 And carrying out plasma etching, setting the temperature to be 700 ℃, and etching for 1.5h to enable dislocation to be exposed. Carrying out homoepitaxial growth of the diamond by adopting a microwave plasma chemical vapor deposition system (MPCVD), putting the treated seed crystal on a deposition table of MPCVD equipment, closing a deposition chamber, vacuumizing the chamber, introducing 300sccm of hydrogen, setting the temperature to 950 ℃, introducing 25sccm of methane gas and 1.2sccm of oxygen after reaching the set temperature, and carrying out diamond growth for 96 hours to obtain a (100) oriented single crystal and a (111) oriented polycrystalline composite diamond; and then, selecting 40W and 20W diamond powder to grind the diamond for 1h until the surface is relatively flat, and performing powder pressing treatment on a polishing machine for 20min each time until the roughness of the crystal surface except the polycrystalline point is 0.46nm. Again using 200 ℃ H 2 SO 4 ＝25ml，HNO 3 Washing with 5ml of acidic mixed solution for 20min, and performing ultrasonic treatment with acetone and alcohol for 5min; putting the treated sample into a Microwave Plasma Chemical Vapor Deposition (MPCVD) device, closing a deposition cavity, and then putting the sample into a vacuum chamberAnd vacuumizing the cavity, wherein the carbon source gas is methane, the boron source gas is trimethyl borate, the set temperature is 1000 ℃, the methane flow rate is 1.5%, the B/C ratio is 1500ppm, the growth time is 3h, and finally the resistance is measured to be 232m omega cm.
Example 3
The dislocation density was selected to be 1.6X 10 6 /cm 2 And diamond (100) CVD seed crystal with the size of 4mm multiplied by 0.5mm is precisely polished by a polishing machine, the polishing machine needs to carry out powder pressing treatment before polishing, each polishing time is 20min, and the polishing time is more than 40min until the RMS value reaches 0.36nm. Placing the seed crystal at 200 deg.C H 2 SO 4 ＝25ml，HNO 3 Washing with 5ml acidic mixed solution for 20min, and ultrasonic treating with acetone and ethanol for 5min. Putting the seed crystal on a deposition table of MPCVD equipment, closing a deposition cavity, vacuumizing the cavity, and introducing H 2 /O 2 And carrying out plasma etching, and setting the temperature to be 750 ℃ for etching for 1h so as to expose dislocation. Carrying out homoepitaxial growth on the diamond by adopting a microwave plasma chemical vapor deposition system (MPCVD), putting the treated seed crystal on a deposition table of MPCVD equipment, closing a deposition chamber, vacuumizing the chamber, introducing 300sccm of hydrogen, setting the temperature to 900 ℃, introducing 20sccm of methane gas and 1.2sccm of oxygen after the temperature reaches the set temperature, and carrying out diamond growth for 120 hours to obtain a (100) oriented single crystal and a (111) oriented polycrystalline composite diamond; and then, selecting 40W and 20W diamond powder to grind the diamond for 1h until the surface is relatively flat, and performing powder pressing treatment on a polishing machine for 20min each time until the roughness of the crystal surface except the polycrystalline point is 0.33nm. Again using 200 ℃ H 2 SO 4 ＝25ml，HNO 3 Cleaning with 5ml acidic mixed solution for 20min, and respectively performing ultrasonic treatment with acetone and alcohol for 5min; putting the treated sample into Microwave Plasma Chemical Vapor Deposition (MPCVD) equipment, closing a deposition cavity, vacuumizing the cavity, wherein the carbon source gas is methane, the phosphorus source gas is phosphine, the set temperature is 950 ℃, the methane flow rate is 1%, the P/C ratio is 1000ppm, the growth time is 3h, and finally, the measured resistance is 20 omega cm
Example 4
Screening out dislocation density of 1.8X 10 6 /cm 2 And diamond (100) CVD seed crystal with the size of 4mm multiplied by 0.5mm is precisely polished by a polishing machine, the polishing machine needs to carry out powder pressing treatment before polishing, each polishing time is 20min, and the polishing time is more than 40min until the RMS value reaches 0.63nm. Placing the seed crystal at 200 deg.C H 2 SO 4 ＝25ml，HNO 3 Washing with 5ml acidic mixed solution for 20min, and ultrasonic treating with acetone and ethanol for 5min. Putting the seed crystal on a deposition table of MPCVD equipment, closing a deposition cavity, vacuumizing the cavity, and introducing H 2 /O 2 And carrying out plasma etching, setting the temperature to be 750 ℃, and etching for 1.5h to enable dislocation to be exposed. Carrying out homoepitaxial growth of the diamond by adopting a microwave plasma chemical vapor deposition system (MPCVD), putting the treated seed crystal on a deposition table of MPCVD equipment, closing a deposition chamber, vacuumizing the chamber, introducing 300sccm of hydrogen, setting the temperature to 950 ℃, introducing 30sccm of methane gas and 1.2sccm of oxygen after the temperature reaches the set temperature, and carrying out diamond growth for 72 hours to obtain the diamond compounded by the (100) oriented single crystal and the (111) oriented polycrystal; and then, selecting 40W and 20W diamond powder to grind the diamond for 1h until the surface is relatively flat, and performing powder pressing treatment on a polishing machine for 20min each time until the roughness of the crystal surface except the polycrystalline point is 0.52nm. Again at 200 ℃ H 2 SO 4 ＝25ml，HNO 3 Cleaning with 5ml acidic mixed solution for 20min, and respectively performing ultrasonic treatment with acetone and alcohol for 5min; putting the steps into an MPCVD device, and adopting a microwave plasma hydrogenation mode, wherein the gas adopts high-purity hydrogen gas (A), (B)>99.9999%), the temperature is 700 ℃, the processing time is 10min, and when the plasma power supply is closed again, the hydrogen is still introduced to the room temperature to avoid the influence of other gases. Finally, the resistance is 2000 omega/sq by Hall test.
Claims (10)
1. A preparation method of a (100)/(111) oriented composite high-performance diamond semiconductor is characterized by comprising the following concrete implementation steps:
step 1: screening of seed crystals
Screening dislocation density greater than 10 6 /cm 2 The diamond (100) oriented seed of (a);
step 2: outcrop of dislocation
Precisely polishing the screened seed crystal by using a polishing machine to obtain surface roughness beneficial to epitaxial growth; removing surface impurities through acid washing and ultrasonic treatment, and then performing plasma etching by using microwave plasma chemical vapor deposition equipment to expose dislocation;
and step 3: (111) Growth of oriented high density polycrystalline dots
The growth process is adjusted through a microwave plasma chemical vapor deposition technology, homoepitaxial growth is carried out, and the formation of high-density (111) oriented polycrystalline points is realized;
and 4, step 4: (100) Formation of single crystal and (111) polycrystalline composites
Grinding and polishing the sample in the step 3 to obtain a (100) single crystal and (111) polycrystalline composite material, and then carrying out acid washing and ultrasonic treatment for epitaxial growth and surface hydrogenation treatment;
and 5: formation of doped or hydrogen terminated diamonds
Similarly, by using a microwave plasma chemical vapor deposition technology, carrying out epitaxial impurity doping growth on the single crystal and polycrystalline composite material processed in the step 4 to form doped diamond, or forming hydrogen terminal diamond by using a microwave plasma hydrogenation mode; the epitaxial doping forms both P-type conductivity and N-type conductivity.
2. The method of producing a (100)/(111) oriented composite high performance diamond semiconductor according to claim 1, wherein the seed screening size in step 1 is 3mm X3 mm to 10mm X10 mm, the seed is selected to be CVD or HTHP, and the average dislocation density of the crystal is calculated using X-ray diffraction peak Full Width Half Maximum (FWHM) fitting.
3. The method of producing a (100)/(111) oriented composite high performance diamond semiconductor according to claim 1, wherein the precise polishing parameters in step 2 are: polishing for 5-10min until RMS value less than 1nm is reached.
4. The method for preparing a (100)/(111) oriented composite high-performance diamond semiconductor according to claim 1, wherein the acid washing and ultrasonic treatment in step 2 comprises the following specific steps: adopts 200-250 ℃ of HNO 3 /H 2 SO 4 =1:3-5, cleaning for 20-40min by using an acidic mixed solution, respectively carrying out ultrasonic treatment for 5-10min by using acetone and alcohol in order to remove surface metal particles and organic impurities, and then drying in a nitrogen atmosphere.
5. The method for preparing a (100)/(111) directionally-compounded high performance diamond semiconductor according to claim 1, wherein the step 2 of exposing dislocations comprises the steps of: putting the treated seed crystal into microwave chemical vapor deposition equipment, and introducing H 2 /O 2 And carrying out plasma etching, wherein the etching temperature is 600-800 ℃, and the etching lasts for at least more than 1h, so that the dislocation is exposed.
6. The method for preparing a (100)/(111) directionally-compounded high performance diamond semiconductor according to claim 1, wherein the specific step of growing the polycrystalline spot in step 3 is: and (2) carrying out homoepitaxial growth of the diamond by adopting a microwave plasma chemical vapor deposition system (MPCVD), putting the treated seed crystal on a deposition table of MPCVD equipment, and carrying out diamond growth at the temperature of more than or equal to 900 ℃ and the methane concentration of more than 5 percent to realize (111) oriented polycrystalline points with different densities.
7. The method for producing a (100)/(111) orientation-compounded high-performance diamond semiconductor according to claim 1, wherein the grinding and polishing in step 4 comprises the steps of: sequentially selecting diamond powder with the grain size from large to small, grinding for 1-1.5h every 10 minutes until the surface is relatively flat; and then performing precise polishing, wherein the polishing machine is subjected to powder pressing treatment before polishing, the polishing time is 20min each time, the polishing time is 1-1.5h, and the crystal surface is polished until the RMS value of the crystal surface except the polycrystalline point reaches less than 1nm.
8. The method for preparing a (100)/(111) oriented composite high-performance diamond semiconductor according to claim 1, wherein the acid washing and ultrasonic treatment in step 4 are performed at 200-250 ℃ by HNO 3 /H 2 SO 4 =1:3-5 of acid mixed solution for 20-40min, respectively carrying out ultrasonic treatment on the metal particles and organic impurities for 5-10min by using acetone and alcohol, and then drying in the nitrogen atmosphere.
9. The method for preparing a (100)/(111) directionally-compounded high performance diamond semiconductor according to claim 1, wherein the epitaxial doping to form P-type conductivity in step 5 comprises the following specific steps: as for B doping, the material treated in the step 4 is placed into Microwave Plasma Chemical Vapor Deposition (MPCVD) equipment, the carbon source gas is methane, and the gas required by the epitaxial growth of B element is doped, wherein the growth temperature is 900-1200 ℃, the methane flow accounts for 0.1-5%, the B/C ratio is 50-50000ppm, and the growth time is more than or equal to 1h;
the specific steps of the epitaxial doping and N-type conductivity forming in the step 5 are as follows: and 3, as for P doping, putting the treated material obtained in the step 4 into Microwave Plasma Chemical Vapor Deposition (MPCVD) equipment, wherein a carbon source gas is methane, and a gas required by epitaxial growth of a P element is doped, wherein the growth temperature is 900-1200 ℃, the methane flow accounts for 0.1-5%, the P/C ratio is 50-50000ppm, and the growth time is more than or equal to 1h.
10. The method for preparing a (100)/(111) orientation-composited high-performance diamond semiconductor according to claim 1, wherein the surface hydrogenation treatment in step 5 comprises the following specific steps: putting the steps into an MPCVD device, adopting a microwave plasma hydrogenation mode, controlling the temperature range to be 650-750 ℃, controlling the processing time to be 8-15min, and keeping the introduction of hydrogen to the room temperature when the plasma power supply is closed again in order to avoid the influence of other gases.
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| CN115573032A (en) * | 2022-10-18 | 2023-01-06 | 北京科技大学 | Method for assembling and synthesizing large-size single crystal diamond |
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