CN101230454A - Method for preparing cubic boron nitride thin film - Google Patents
Method for preparing cubic boron nitride thin film Download PDFInfo
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- CN101230454A CN101230454A CNA200710304789XA CN200710304789A CN101230454A CN 101230454 A CN101230454 A CN 101230454A CN A200710304789X A CNA200710304789X A CN A200710304789XA CN 200710304789 A CN200710304789 A CN 200710304789A CN 101230454 A CN101230454 A CN 101230454A
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Abstract
The invention relates to a method of preparing a cubic boron nitride film and belongs to the field of wide-band-gap semiconductor or superhard material films. The problems with the direct preparation of a boron nitride film with a high cubic-phase content are that the technique is hard to be controlled and the repeatability is poor, that energy particles must be adopted to bombard the film surface during the nucleation and growth of the cubic boron nitride film, which generates structural defects for the film, and that the film has an excessive strong remaining stress and is easy to become chapped and fall off. The invention has the following steps: firstly, an underlay is cleaned and a gaseous-phase film-growing device is used on the underlay material to deposit a hexagonal boron nitride film; secondly, the vacuum degree is vacuumized to be below 5Pa and the hexagonal boron nitride film is annealed under the protection of the nitrogen gas with an annealing temperature of 850 to 950 DEG C for 20 to 60 minutes at a constant temperature. The purity quotient of the nitrogen gas is over 99.999 percent. The invention has loose conditions and good repeatability, no underlay heating device or underlay negative bias device is needed to generate energy particles to bombard the film and no optimal working barometric pressure or component is needed. In addition, the hexagonal boron nitride film has higher deposition rate and is hard to become chapped and fall off.
Description
Technical field
The present invention relates to the preparation method that a kind of vapour deposition of cubic boron nitride film combines with annealing process.Belong to wide band gap semiconducter or superhard material film preparation field.
Background technology
Boron nitride (BN) is a kind of Wideband gap semiconductor material.In the boron nitride system, hexagonal boron nitride (h-BN) and cubic boron nitride (c-BN) are two stable principal phases.Wherein have outstanding physics, chemistry, mechanical property with cubic boron nitride especially.Therefore, about its material preparation and characteristic research, and the exploration of industrialization, device is various countries' researcher in recent years always, and such as U.S. G.E, IBM, the research topic of well-known semiconductor company common concerns such as Britain DeBeers.
Hardness, the thermal conductivity of cubic boron nitride are only second to diamond; And its resistance to chemical corrosion and high temperature oxidation resistance obviously are better than diamond, and especially it has affinity with iron family element ting unlike diamond, is more suitable for iron family metal materials processing; Now, its machinery of the main focus utilization of the practicability of cubic boron nitride and mechanical property are widely used in the superhard coating of grinding tool, cutter, instrument, accurate window supercoat, lathe, space flight, fields such as military project.In addition, cubic boron nitride has and now knows the wideest forbidden band (particle E
g≈ 6.4eV; Film E
g≈ 6.0eV), therefore very high light transmission rate can be arranged in very wide spectral range.It can realize that also n type and p type mix, so cubic boron nitride can prepare transparent under special environment, high temperature, high frequency, high-power, radioprotective short wavelength light electron device.
The cubic boron nitride occurring in nature does not exist, and needs synthetic.Nineteen fifty-seven, the Wentorf of U.S. G.E company has synthesized cubic boron nitride powder first with high temperature and high pressure method (HTHP).Yet, high temperature and high pressure method equipment requirements harshness, and can only prepare cubic boron nitride particle, particle scale little (being up to the mm magnitude) makes industrial applications be subjected to great restriction.A kind of semi-conductor, superhard material will be realized purposes and device, microminiaturized with regard to the necessary filming that realizes it widely.In 1979, the Sokolowski reported first used low pressure gas phase deposition to synthesize the cubic boron nitride film that has more application prospect.Two during the last ten years, and the various countries investigator directly deposits the prepared in laboratory that has realized cubic boron nitride film by multiple physics, chemical gas phase, but exploring always a kind of high cube of content boron nitride pellicle easily, low-cost, preparation method capable of being industrialized.
The vapour deposition that generally believes cubic boron nitride film need be experienced two stages of nucleation and growth, and nucleation stage plays a decisive role.Yet the parameter window of nucleation stage is extremely narrow, needs to be provided with substrate negative film pressure device simultaneously, the bombardment of generate energy ion pair film surface, and very big for different preparation methods and experimental installation otherness.This can produce many factors that are unfavorable for cubic boron nitride film practicability, directly prepares high cube phase content boron nitride pellicle technology controlling and process difficulty such as vapour deposition; Problems such as preparation poor repeatability.These factors make cubic boron nitride film become in the boron nitride the most difficult direct preparation, are restricting the process that cubic boron nitride film moves towards the industrialization from the laboratory all the time.In order to address these problems; we can change the hexagonal boron nitride film that is very easy to prepare into high-quality cubic boron nitride film inventing first and having realized protecting annealing process by the high pure nitrogen of physics or chemical vapour deposition and specified temp.Present method is not at home and abroad appeared in the newspapers as yet.
Summary of the invention
The present invention relates to a kind of method for preparing cubic boron nitride film.The first step earlier prepares one deck hexagonal boron nitride film by physics or chemical gaseous phase depositing process, loose preparation condition, and according to the Ostwald-Volmer theory, low density is easier nucleating growth in deposition process.So the preparation condition that this step adopts is looser than the preparation condition of direct preparation cubic boron nitride film, and good reproducibility (need not to be provided with the substrate warming apparatus; Need not to be provided with the substrate DC bias device with of the bombardment of generate energy particle to film; Need not to select for use best working gas air pressure and component.Do not consider equipment failure, can realize 100% repeatability, and the hexagonal boron nitride film deposition rate is faster, being difficult for being chapped from the cold comes off).Second step was carried out specific high pure nitrogen protection annealing to the hexagonal boron nitride film again, made six side's phase boron nitrides in the film become cubic boron nitride mutually.
Purpose of the present invention can realize by following techniqueflow:
The first step: substrate is carried out using film vapor phase growth equipment (for example rf magnetron sputtering, electron cyclotron resonance chemical vapor deposition etc.) deposition one deck hexagonal boron nitride film after routine cleans on substrate material.
Described substrate material can be silicon single crystal (Si), diamond, nickel (Ni), steel, titanium (Ti), copper (Cu), SiC, WC, high rigidity such as TiN, the material of high-melting-point (950 ℃ softening transform can not take place).
The thickness of this layer hexagonal boron nitride film can be according to the sedimentation rate and the depositing time control of different film growth apparatus.After second step process, film thickness has minimizing, because the density of cubic boron nitride is greater than hexagonal boron nitride, after undergoing phase transition, due to the volumetric shrinkage.
Second step: the hexagonal boron nitride film is carried out high pure nitrogen protection annealing.Annealing temperature is 850～950 ℃; Constant temperature 20～60 minutes; Shielding gas is high pure nitrogen (purity 99.999%).
Purpose is: make hexagonal boron nitride in the film gradually to the most stable cubic boron nitride phase transformation; Reduce textural defect, improve film quality; Discharge membrane stress, increase the adhesivity of film and substrate, help film work-ing life; By depositing the hexagonal boron nitride film earlier, become cubic boron nitride film mutually, reduce directly to prepare the technology difficulty of cubic boron nitride film, improved the repeatability of cubic boron nitride film preparation greatly.
The high pure nitrogen (purity 99.999%) of Annealing Protection gas provided by the invention for buying.Reason is that the boron atom ratio nitrogen-atoms is easier of substrate surface in vapour deposition, therefore the general rich boron of boron nitride pellicle of preparation.Impurity effect had both been avoided in the protection of use high pure nitrogen, increased the nitrogen element ratio in the film again, promoted the easier cubic boron nitride that becomes mutually of hexagonal boron nitride.
Nitrogen pressure in furnace should keep malleation (overgauge normal atmosphere) during annealing, and purpose is to prevent that air from infiltrating the impurity effect phase transformation.Treat to begin to heat up behind the steady air current, constant temperature finishes the back and reduces to room temperature naturally, and whole annealing process continues ventilation.
Cube phase content is greater than 70% in the cubic boron nitride film of the present invention's preparation.(the spectrograph model is: WQF-310) measure cube phase content in the BN film to adopt the fourier infrared transmitted spectrum (FTIR) that generally uses.
Embodiment
Further introduce the present invention with following example.The ratio of working gas is volume ratio in following examples form.
Example one
Step 1: preparation hexagonal boron nitride film in radio frequency (13.56Hz) sputtering system.Sputtering system adopts high-purity hexagonal boron nitride (99.99%) hot pressing target.This example adopt the most frequently used monocrystalline polished silicon slice of semicon industry as substrate (for example: the n type, resistivity 2～4 Ω cm, thickness is 0.3～0.5mm).Before deposition, substrate passes through toluene, acetone, ethanol respectively, 20% hydrofluoric acid solution (hydrofluoric acid and deionized water volume ratio be mix at 1: 4) and deionized water ultrasonic cleaning.The concrete growthing process parameter of this example film is listed in the table 1
| Preliminary vacuum degree (* 10 -3pa) | Depositing time (mins) | Working gas (Ar/N 2) | Operating air pressure (Pa) | Power (W) |
| ＜2 | 240 | 5∶1 | 1.5 | 400 |
Prepared hexagonal boron nitride film thickness is about 2 μ m.
Step 2: the hexagonal boron nitride film is carried out nitrogen protection annealing.Annealing furnace feeds high pure nitrogen (99.999%), behind the steady air current, begins to heat up, and after 60 minutes, cools to room temperature in 850 ℃ of insulations of temperature naturally, the omnidistance lasting nitrogen that feeds.
A cube phase content is about 75% in the gained cubic boron nitride film.
Example two
Step 1: preparation hexagonal boron nitride film in radio frequency (13.56Hz) sputtering system.Equipment and substrate pre-treatment are the same.The concrete growthing process parameter of this example film is listed in the table 2
| Preliminary vacuum degree (* 10 -3pa) | Depositing time (mins) | Working gas (Ar/N 2) | Operating air pressure (Pa) | Power (W) |
| ＜2 | 60 | 3∶1 | 1 | 300 |
Prepared hexagonal boron nitride film thickness is about 300nm.
Step 2: the hexagonal boron nitride film of gained is carried out 900 ℃ of insulations high pure nitrogen protection in 40 minutes annealing.
A cube phase content is about 92% in the gained cubic boron nitride film.
Example three
Step 1: preparation hexagonal boron nitride film in radio frequency (13.56Hz) sputtering system.Equipment and substrate pre-treatment are the same.The concrete growthing process parameter of this example film is listed in the table 3
| Preliminary vacuum degree (* 10 -3pa) | Depositing time (mins) | Working gas (Ar/N 2) | Operating air pressure (Pa) | Power (W) |
| ＜2 | 120 | 4∶1 | 1.3 | 300 |
Prepared hexagonal boron nitride film thickness is about 700nm.
Step 2: the hexagonal boron nitride film of gained is carried out 950 ℃ of insulations high pure nitrogen protection in 20 minutes annealing.
A cube phase content is about 87% in the gained cubic boron nitride film.
Example four
Step 1: utilize electron cyclotron resonance chemical vapor deposition hexagonal boron nitride film.This example film growth main technologic parameters is listed in the table 4
| Preliminary vacuum degree (* 10 -3pa) | Depositing time (mins) | Working gas BF 3∶Ar∶He∶N 2 | Operating air pressure (Pa) | Microwave power (W) |
| ＜4 | 60 | 1∶20∶2∶40 | 1.3 | 700 |
Prepared hexagonal boron nitride film thickness is about 450nm.
Step 2: the hexagonal boron nitride film of gained is carried out 900 ℃ of insulations high pure nitrogen protection in 40 minutes annealing.
A cube phase content is about 72% in the gained cubic boron nitride film.
Example five
Step 1: preparation hexagonal boron nitride film in magnetic control sputtering system.This example film growth main technologic parameters is listed in the table 5
| Preliminary vacuum degree (* 10 -3pa) | Depositing time (mins) | Working gas (Ar/N 2) | Operating air pressure (Pa) | Power (W) |
| ＜2 | 45 | 3∶1 | 0.6 | 150 |
Prepared hexagonal boron nitride film thickness is about 100nm
Step 2: the hexagonal boron nitride film of gained is carried out 950 ℃ of insulations high pure nitrogen protection in 30 minutes annealing.
A cube phase content is about 95% in the gained cubic boron nitride film.
Claims (1)
1. the preparation method of a cubic boron nitride film is characterized in that, may further comprise the steps:
1), on substrate material, uses gas phase membrane growth apparatus deposition one deck hexagonal boron nitride film with after the substrate cleaning;
2) vacuum tightness is extracted into below the 5Pa, the nitrogen protection of hexagonal boron nitride film is annealed: annealing temperature is 850～950 ℃, constant temperature 20～60 minutes; Described nitrogen is that purity is more than 99.999%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807519A (en) * | 2010-03-22 | 2010-08-18 | 吉林大学 | Method for preparing cubic boron nitride single crystal-film homogeneous P-N junction |
| CN102212788A (en) * | 2011-06-10 | 2011-10-12 | 北京工业大学 | Method for preparing boron nitride film containing nano-silver particles |
| CN103541000A (en) * | 2013-11-06 | 2014-01-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Device and method for preparing boron nitride single crystal |
| CN103774113A (en) * | 2014-02-24 | 2014-05-07 | 中国科学院上海微系统与信息技术研究所 | Method for preparing hexagonal boron nitride film |
| CN105568253A (en) * | 2016-01-06 | 2016-05-11 | 复旦大学 | Method for growing hexagonal boron nitride by plasma chemical vapor deposition equipment |
| CN108101547A (en) * | 2017-12-22 | 2018-06-01 | 北京富兴凯永兴光电技术有限公司 | Optical filming material and preparation method thereof |
| CN111362703A (en) * | 2020-03-30 | 2020-07-03 | 中原工学院 | Polycrystalline cubic boron nitride cutter sintered at low pressure and preparation method |
| CN111710752A (en) * | 2020-06-24 | 2020-09-25 | 吉林大学 | MSM type deep ultraviolet photoelectric detector based on cubic boron nitride thick film and preparation method |
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| CN106399938A (en) * | 2016-10-20 | 2017-02-15 | 富耐克超硬材料股份有限公司 | Preparation method for cubic boron nitride film |
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- 2007-12-28 CN CNB200710304789XA patent/CN100558933C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807519A (en) * | 2010-03-22 | 2010-08-18 | 吉林大学 | Method for preparing cubic boron nitride single crystal-film homogeneous P-N junction |
| CN102212788A (en) * | 2011-06-10 | 2011-10-12 | 北京工业大学 | Method for preparing boron nitride film containing nano-silver particles |
| CN103541000B (en) * | 2013-11-06 | 2016-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of device and method preparing boron nitride monocrystal |
| CN103541000A (en) * | 2013-11-06 | 2014-01-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Device and method for preparing boron nitride single crystal |
| WO2015067029A1 (en) * | 2013-11-06 | 2015-05-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Device and method for preparing boron nitride monocrystals |
| CN103774113A (en) * | 2014-02-24 | 2014-05-07 | 中国科学院上海微系统与信息技术研究所 | Method for preparing hexagonal boron nitride film |
| CN103774113B (en) * | 2014-02-24 | 2015-10-28 | 中国科学院上海微系统与信息技术研究所 | A kind of method preparing hexagonal boron nitride film |
| CN105568253A (en) * | 2016-01-06 | 2016-05-11 | 复旦大学 | Method for growing hexagonal boron nitride by plasma chemical vapor deposition equipment |
| CN105568253B (en) * | 2016-01-06 | 2018-12-11 | 复旦大学 | A kind of method of apparatus for plasma chemical vapor deposition growth hexagonal boron nitride |
| CN108101547A (en) * | 2017-12-22 | 2018-06-01 | 北京富兴凯永兴光电技术有限公司 | Optical filming material and preparation method thereof |
| CN111362703A (en) * | 2020-03-30 | 2020-07-03 | 中原工学院 | Polycrystalline cubic boron nitride cutter sintered at low pressure and preparation method |
| CN111362703B (en) * | 2020-03-30 | 2022-03-25 | 中原工学院 | Polycrystalline cubic boron nitride cutter sintered at low pressure and preparation method |
| CN111710752A (en) * | 2020-06-24 | 2020-09-25 | 吉林大学 | MSM type deep ultraviolet photoelectric detector based on cubic boron nitride thick film and preparation method |
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