CN101807519A - Method for preparing cubic boron nitride single crystal-film homogeneous P-N junction - Google Patents
Method for preparing cubic boron nitride single crystal-film homogeneous P-N junction Download PDFInfo
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Abstract
The invention relates to a method for preparing cubic boron nitride (cBN) single crystal-film homogeneous P-N junction, and belongs to a method for preparing semiconductor components. The method comprises the steps of: synthesizing a semiconducting cBN single crystal with semiconductor characteristic and preparing a doped cBN film, wherein the cBN film has the semiconductor characteristic opposite to that of the cBN single crystal; the semiconducting cBN single crystal with the semiconductor characteristic is synthesized by a high-pressure direct synthesis method or a high-pressure re-diffusion method; and the doped cBN film is prepared by taking the semiconducting cBN single crystal with the semiconductor characteristic as a substrate and doping and growing a cBN film with a semiconductor type opposite to a substrate type by a vacuum vapor deposition method. The vacuum vapor deposition method is a vacuum physical vapor deposition method or a vacuum chemical vapor deposition method. The method has the advantages of reduction in processing difficulties, improvement on production efficiency, yield and the like and great improvement compared with the conventional technology for preparing a cBN homogeneous P-N junction by high-pressure systemization and re-growth processes.
Description
Technical field
The invention belongs to the preparation method of semiconductor element, the preparation method of particularly a kind of cubic boron nitride monocrystal-film homogeneous P-N junction.
Background technology
Cubic boron nitride (cBN) is a kind of pure artificial synthetic multifunctional material.It not only has and is only second to adamantine hardness, is a kind of at the widely used superhard material of field of machining, and the cBN crystal still is a typical III-V family semiconductor.CBN can tolerate the wideest direct band gap of 1200 ℃ of high temperature, about 6.4eV, can be doped to character such as N-and P-N-type semiconductor N material, and these excellent properties are having a wide range of applications it aspect the high temperature resistant large power semiconductor device.
Yet the cBN monocrystal is normally synthetic under the extreme condition of high pressure high temperature (～5Gpa ,～1500 ℃), and crystal growth is very difficult.So far with high temperature and high pressure method synthetic maximum sized monocrystalline under laboratory condition 3mm is only arranged in the world, this brings very big difficulty for the research and the application of cBN characteristic of semiconductor.Current, U.S. Patent No. 3078232 points out that a spot of Be element that mixes in the cBN crystal that height is pressed into has P-N-type semiconductor N character; U.S. Patent No. 3141802 and No.3216942 point out to have N-N-type semiconductor N character more than a kind of the reaching in mix in the cBN crystal that height is pressed into a spot of Si, Ge, S or the Se element.Based on the above-mentioned character of cBN crystal, Japanese scholar O.Mishima in 1987 deliver the article of relevant cBN homogeneous P-N junction on " Science " 238 (1987) 181, have occurred several pieces of patents of making about the cBN homogeneous P-N junction subsequently again.The method of its making is roughly:
(1), the boron nitride source and the catalyst that will be mixed with the Be element carry out high temperature high pressure process, the synthetic bulky grain cBN monocrystalline that obtains is owing to the substitution effect of Be atom presents P-N-type semiconductor N character;
(2), with the P-type cBN monocrystalline that obtains in the regulations (1) as seed crystal, be put in a kind of and above the BN source and catalyst that is mixed with in Si, Ge, S or the Se element, adopt the method for temperature gradient, under high-temperature and high-pressure conditions, regrowth obtains having the cBN single-crystal surface of N-N-type semiconductor N characteristic, like this, experiment makes the homogeneous P-N junction of cBN.
Certainly, also can synthesize the cBN seed crystal of N-type earlier, high pressure growth P-type cBN surface can access the cBN homogeneous P-N junction equally again.Yet, above-mentionedly prepare the P-N knot by the long method of high-pressure regeneration and have the following disadvantages: (1), height be pressed into and the regrowth cBN monocrystalline time long, production efficiency is low; (2), the cBN homogeneous P-N junction that is pressed into of height must be through cutting, grind, and just can carry out actual application, granularity be become specific shape at little and very hard again cBN crystal-cut, technology difficulty is very big, corresponding rate of finished products is low, cost increases; (3), semiconductor doping only is confined to the initial feed of height before being pressed into, the doping in the building-up process is uncontrollable, and the combination that is difficult to realize the deposition of multilayer film and prepares various devices; (4) since high be pressed into cBN single crystal grain surface irregularity, cause the interface roughness of P-N knot, resist that to wear voltage not high.
Summary of the invention
The present invention is for overcoming the deficiencies in the prior art, the preparation method of a kind of cubic boron nitride monocrystal-film homogeneous P-N junction is provided, this method has reduced technology difficulty, has reduced technical process, production efficiency and rate of finished products have been improved, reduced production cost simultaneously, the interface of the P-N knot of preparing is smooth, has improved the anti-breakdown of cBN homogeneous P-N junction.
Technical scheme of the present invention is: at first, height be pressed into the cBN monocrystalline in the form of sheets, rather than synthetic bulky grain cBN monocrystalline, through the cutting again after the PROCESS FOR TREATMENT.This synthetic be on cubic hinge press, to realize that by the suitable temperature and pressure gradient of control inside cavity the cBN single-chip size of acquisition is at 300～500 microns, thickness is at tens to tens microns, the surface is (111) face.Before carrying out the cBN film growth, the cBN sheet is cleaned completely.Mixed liquor with ethanol and acetone carries out ultrasonic cleaning earlier, and the mixed solution with nitric acid and hydrochloric acid carries out chemical cleaning then, cleans with deionized water at last and the infrared lamp oven dry.
Secondly, adopt the cBN film of the method preparation doping of vapour deposition, rather than the synthetic regenerated long cBN film of high pressure, be that the cBN single-chip is put into vacuum chamber, carry out doped growing cBN film by the means of vacuum deposition film, make that the cBN film that grows is opposite with the semiconductor type of cBN single-chip, be prepared into cBN monocrystalline-film homogeneous P-N junction.Owing to adopt the method for vapour deposition, can in time adjust in the deposition process, the concentration of controlled doping material, can also utilize means such as modern photoetching, mask to realize the integrated of devices.
Concrete processing step of the present invention comprises: synthetic have the cBN single-chip of characteristic of semiconductor and prepare the cBN film that mixes, described synthetic cBN single-chip with characteristic of semiconductor, be to adopt the method that high pressure is directly synthetic or high pressure spreads again, the direct synthetic method of described high pressure is to be mixed with Si, the hexagonal boron nitride (hBN) of semiconductor impurities elements such as Be is a raw material, with containing lithium, the catalyst of boron and nitrogen element, in 1800～2000K temperature, 5.0 under～6.5GPa the condition, pressurize is 3～40 minutes in the cubic hinge press cavity, the directly synthetic cBN single-chip that obtains N-or P-type; Described high pressure method of diffusion again is to be that raw material adopts above-mentioned technical process to synthesize pure cBN single-chip with pure hBN, again the cBN single-chip of clean is imbedded in the crucible of elements such as Si, Be are housed, in high-temperature vacuum, spread, the vacuum chamber internal gas pressure is controlled at 0.5～1.0Pa, temperature is at 1200～1400K, spread 0.5～1.0 hour, the cold naturally again room temperature that goes to, the cBN single-chip that makes height be pressed into has characteristic of semiconductor.
The cBN film that described preparation is mixed, the cBN single-chip that is pressed into, has characteristic of semiconductor with height is a substrate, utilize the method for vapour deposition cBN films such as rf magnetron sputtering physical vapour deposition (PVD) RF-PVD method, inductively coupled plasma chemical vapour deposition (CVD) ICP-CVD method, cBN film in cBN single-chip superficial growth doping, make that the cBN film that grows is opposite with the semiconductor type of cBN single-chip, prepare cBN monocrystalline-film homogeneous P-N junction.
The inventive method adopts the high method that gentle phase deposition technique combines that is pressed into, preparation cBN monocrystalline-film homogeneous P-N junction, it has reduced technology difficulty, has improved production efficiency and rate of finished products etc., and height in the past is pressed into, regrowth prepares cBN homogeneous P-N junction technology and improves a lot.
The quality of P-N knot is directly related with the cBN growth for Thin Film, and even epitaxially grown cBN film helps the raising of P-N knot quality, if there are thicker transition zone in the cBN film of growth and substrate, then can produce harmful effect to the P-N knot.
Embodiment:
Embodiment 1 high pressure direct synthesis technique is synthesized P-type cBN single-chip
With the hexagonal boron nitride that is mixed with 1～5%Be element is raw material, contain lithium, boron and nitrogen element in the catalyst, temperature is controlled at 1820K, pressure is controlled at 5.2GPa, pressurize is 40 minutes in the cubic hinge press cavity, obtains P-N-type semiconductor N characteristic, ganoid, the cBN single-chip that is about 300～500 micron-scales.
Embodiment 2 high pressure direct synthesis techniques are synthesized P-type cBN single-chip
With the hexagonal boron nitride that is mixed with 1～5%Be element is raw material, contain lithium, boron and nitrogen element in the catalyst, temperature is controlled at 1870K, pressure is controlled at 6.0GPa, pressurize is 25 minutes in the cubic hinge press cavity, obtains P-N-type semiconductor N characteristic, ganoid, the cBN single-chip that is about 300～500 micron-scales.
Embodiment 3 high pressure direct synthesis techniques are synthesized P-type cBN single-chip
With the hexagonal boron nitride that is mixed with 1～5%Be element is raw material, contain lithium, boron and nitrogen element in the catalyst, temperature is controlled at 1950K, pressure is controlled at 6.2GPa, pressurize is 15 minutes in the cubic hinge press cavity, obtains P-N-type semiconductor N characteristic, ganoid, the cBN single-chip that is about 300～500 micron-scales.
The method that embodiment 4 high pressure spread is again synthesized N-type cBN single-chip
With pure hexagonal boron nitride is raw material, with the catalyst that contains lithium, boron and nitrogen element, under 1820K temperature, 5.2G P a condition, pressurize is 40 minutes in the cubic hinge press cavity, obtains the ganoid pure cBN single-chip that is about 300～500 micron-scales of zincblende type.After clean, imbed in the graphite crucible that the Si powder is housed, in high-temperature vacuum, spread, the vacuum chamber internal gas pressure is controlled at 1.0Pa, and temperature spread 1.0 hours at 1200K, naturally the cold room temperature that goes to is taken out the afterwash drying, gets the cBN single-chip of N-N-type semiconductor N character.
The method that embodiment 5 high pressure spread is again synthesized N-type cBN single-chip
With pure hexagonal boron nitride is raw material, with the catalyst that contains lithium, boron and nitrogen element, under 1870K temperature, 6.0GPa condition, pressurize is 25 minutes in the cubic hinge press cavity, obtains the ganoid pure cBN single-chip that is about 300～500 micron-scales of zincblende type.After clean, imbed in the graphite crucible that the Si powder is housed, in high-temperature vacuum, spread, the vacuum chamber internal gas pressure is controlled at 1.0Pa, and temperature spread 1.0 hours at 1300K, naturally the cold room temperature that goes to is taken out the afterwash drying, gets the cBN single-chip of N-N-type semiconductor N character.
The method that embodiment 6 high pressure spread is again synthesized N-type cBN single-chip
With pure hexagonal boron nitride is raw material, with the catalyst that contains lithium, boron and nitrogen element, under 1950K temperature, 6.2GPa condition, pressurize is 15 minutes in the cubic hinge press cavity, obtains the ganoid pure cBN single-chip that is about 300～500 micron-scales of zincblende type.After clean, imbed in the graphite crucible that the Si powder is housed, in high-temperature vacuum, spread, the vacuum chamber internal gas pressure is controlled at 1.0Pa, and temperature spread 1.0 hours at 1400K, naturally the cold room temperature that goes to is taken out the afterwash drying, gets the cBN single-chip of N-N-type semiconductor N character.
Embodiment 7 carries out the preceding thorough cleaning that the cBN single-chip is carried out of thin film deposition
With height be pressed into the sheet cBN single-chip mixed liquor of putting into ethanol and acetone earlier carried out ultrasonic cleaning 40 minutes, and then boiled in the mixed solution of nitric acid and hydrochloric acid 2 hours, clean with deionized water at last and the infrared lamp oven dry.
The embodiment 8 rf magnetron sputtering physical vapour deposition (PVD) RF-PVD methods N-type cBN film of on P-type cBN single-chip, growing
The hexagonal boron nitride sheet that is 50mm with the diameter, mixes 5%Si is as sputtering target material, at vacuum chamber by forvacuum to 4 * 10
-3When Pa is above, feeds purity and be higher than 99.99% Ar and N
2Mist, operating air pressure 1～3Pa in the vacuum chamber, N
2With the ratio of Ar 1: 10～1: 20, the bias voltage of use-400～-200V, 200～450 ℃ of base reservoir temperatures, radio frequency sputtering power 100～200W, sedimentation time are 2～4 hours.The surface regeneration of P type cBN single-chip has been grown the cBN film of N type, makes cBN monocrystalline-film homogeneous P-N junction.
The embodiment 9 inductively coupled plasma chemical vapour deposition (CVD) ICP-CVD methods P-type cBN film of on N-type cBN single-chip, growing
At vacuum chamber by forvacuum to 4 * 10
-3After Pa is above, adopt the plasma of H and N that substrate surface and vacuum chamber inwall are cleaned before the deposition earlier, again by mass flowmenter control Ar, N
2And 10%B
2H
6The input variable of (He dilution) gas, wherein Ar gas flow 3～20sccm, N
2Gas flow 1～5sccm, 10%B
2H
6(He dilution) gas flow 1～10sccm, frequency is power 0.3～1.0KW of 13.56MHz, and keeping the operating air pressure in the vacuum chamber is 1～3Pa, and bias voltage is-200～0V, and base reservoir temperature is 200～500 ℃, sedimentation time is 10～30 minutes.The cBN film of deposition shows P-N-type semiconductor N character because of rich B, and the surface regeneration of N-type cBN single-chip has been grown the cBN film of P-type, makes cBN monocrystalline-film homogeneous P-N junction.
Claims (2)
1. the preparation method of cubic boron nitride monocrystal-film homogeneous P-N junction, this method includes: the cubic boron nitride film that the cubic boron nitride monocrystal sheet of synthesized semiconductor characteristic and preparation are mixed, this cubic boron nitride film is opposite with the characteristic of semiconductor of cubic boron nitride monocrystal sheet, it is characterized in that: the cubic boron nitride monocrystal sheet of described synthesized semiconductor characteristic, be to adopt the method that high pressure is directly synthetic or high pressure spreads again, the direct synthetic method of described high pressure is to be raw material with the hexagonal boron nitride that is mixed with the semiconductor impurities element, with containing lithium, the catalyst of boron and nitrogen element, in 1800～2000K temperature, 5.0 under～6.5GPa the condition, pressurize is 3～40 minutes in the cubic hinge press cavity, the directly synthetic cBN single-chip that obtains N-or P-type; Described high pressure method of diffusion again is to be raw material with pure hexagonal boron nitride, with containing lithium, the catalyst of boron and nitrogen element, in 1800～2000K temperature, 5.0 under～6.5GPa the condition, pressurize is 3～40 minutes in the cubic hinge press cavity, the directly synthetic cubic boron nitride monocrystal sheet that obtains N-or P-type, cubic boron nitride monocrystal sheet after will cleaning is again imbedded in the crucible that the semiconductor impurities element is housed, in high-temperature vacuum, spread, the vacuum chamber internal gas pressure is controlled at 0.5～1.0Pa, temperature is at 1200～1400K, spread 0.5～1.0 hour, and naturally cooled to room temperature, the cubic boron nitride monocrystal sheet that makes height be pressed into has N-or P-N-type semiconductor N characteristic;
The cubic boron nitride film that described preparation is mixed is to be substrate with above-mentioned cubic boron nitride monocrystal sheet with characteristic of semiconductor, adopts the method for vacuum vapor deposition, the cubic boron nitride film that the doped growing semiconductor type is opposite with substrate type.
2. according to the preparation method of the described cubic boron nitride monocrystal of claim 1-film homogeneous P-N junction, the method that it is characterized in that described vacuum vapor deposition is physical vacuum vapour deposition process or vacuum chemistry vapour deposition process.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012481A (en) * | 2017-04-14 | 2017-08-04 | 河南工业大学 | A kind of preparation method of new solid solution film/metal hetero-junction optoelectronic pole |
| CN113990724A (en) * | 2021-10-19 | 2022-01-28 | 山西大学 | Full-two-dimensional vacuum tube and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206931A (en) * | 1998-08-22 | 1999-02-03 | 吉林大学 | Method for preparing cubic boron nitride monocrystal-diamond film hetru P-N junction |
| CN101230454A (en) * | 2007-12-28 | 2008-07-30 | 北京工业大学 | Method for preparing cubic boron nitride thin film |
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- 2010-03-22 CN CN 201010128715 patent/CN101807519A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206931A (en) * | 1998-08-22 | 1999-02-03 | 吉林大学 | Method for preparing cubic boron nitride monocrystal-diamond film hetru P-N junction |
| CN101230454A (en) * | 2007-12-28 | 2008-07-30 | 北京工业大学 | Method for preparing cubic boron nitride thin film |
Non-Patent Citations (1)
| Title |
|---|
| 《Science and Technology of New Diamond》 19901231 Osamu MISHIMA CUBIC BORON NITRIDE PN JUNCTION DIODE MADE AT HIGH PRESSURE AS A HIGH TEMPERATURE DIODE AND AN ULTRAVIOLET LED 297-300 , 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012481A (en) * | 2017-04-14 | 2017-08-04 | 河南工业大学 | A kind of preparation method of new solid solution film/metal hetero-junction optoelectronic pole |
| CN107012481B (en) * | 2017-04-14 | 2019-03-12 | 河南工业大学 | A kind of preparation method of solid solution film/metal hetero-junction optoelectronic pole |
| CN113990724A (en) * | 2021-10-19 | 2022-01-28 | 山西大学 | Full-two-dimensional vacuum tube and preparation method thereof |
| CN113990724B (en) * | 2021-10-19 | 2024-03-12 | 山西大学 | Full two-dimensional vacuum tube and preparation method thereof |
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Application publication date: 20100818 |