CN101441997B - N type doping method for cubic boron nitride film - Google Patents
N type doping method for cubic boron nitride film Download PDFInfo
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- CN101441997B CN101441997B CN2007101777830A CN200710177783A CN101441997B CN 101441997 B CN101441997 B CN 101441997B CN 2007101777830 A CN2007101777830 A CN 2007101777830A CN 200710177783 A CN200710177783 A CN 200710177783A CN 101441997 B CN101441997 B CN 101441997B
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- ion
- boron nitride
- nitride film
- cubic boron
- film
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Abstract
The invention relates to a method for n type doping of a cubic boron nitride(c-BN) film, which specifically comprises the following steps: firstly, using an Ion Beam Assisted Depostion (IBAD) method for preparing a high-quality c-BN film; secondly, sequentially injecting S ions with different energy (50, 80 and 100KeV) and total dose of 5*10<14>cm<-2> into the c-BN film; and finally achieving then type doping of the c-BN film. The method has no special requirement on growth equipment of the c-BN film, and has the advantages of capability of precisely controlling doping dose and dosing depth,low cost, convenient method, wide application, good portability and so on.
Description
Technical field
The present invention relates to technical field of semiconductors, particularly relate to a kind of method that realizes that cubic boron nitride film n type mixes.
Background technology
Cubic boron nitride (c-BN) is the III-V group iii v compound semiconductor material of a kind of superhard, broad-band gap, high heat conductance, high resistivity, high thermal stability and chemical stability.It is be known as third generation semi-conducting material after silicon, germanium and GaAs of diamond, carborundum and gallium nitride, wherein the combination property with c-BN is the most excellent again for this, is having a wide range of applications aspect high temperature, high frequency, the high-power electronic device.Shortcomings such as pure c-BN film belongs to insulator, exists the resistivity height, and carrier concentration is low have limited its application in field of microelectronic devices.Have only means, reduce its resistivity, improve carrier concentration and could realize its application in high temperature, high frequency, high power device field by mixing.Therefore, expansion is to realize the basis of c-BN as the high-temperature electronic material to the research of effective doping of c-BN film, and extremely important meaning is arranged.
Utilize methods such as energetic ion injection, diffusion of impurities and synchronous growth doping, people have realized the doping to multiple semiconductor film material, and have promoted the development of microelectronics and opto-electronic device.But because the difficulty of c-BN film in material preparation, at present people are scarcely out of swaddling-clothes to the research of aspects such as the doping of c-BN thin-film material and electrical properties, be embodied as: the means of doping are limited, majority takes synchronous growth to mix, and this proposes higher requirement to film growth apparatus; Doped chemical is single, only limits to elements such as common Be, Mg, C, Si.The method of utilizing ion to inject the S ion realizes the research to the c-BN film doping, yet there are no report.Common method to c-BN film doping S is that synchronous growth is mixed, and for ion injected S, synchronous growth was mixed equipment is proposed higher requirement, and simultaneously, the dopant dose of S is control not too easily also.Ion injects the method for carrying out semiconductor doping does not have specific (special) requirements to c-BN growth for Thin Film equipment, and the degree of depth of its dopant dose and doping can accurately be controlled, and the damage that is caused by the ion injection also can be eliminated by thermal annealing.Therefore, the method for utilizing ion to inject S realizes that the n type doping of c-BN film is had incomparable superiority with respect to existing synchronous growth doping.
Summary of the invention
At the current present situation that the c-BN thin-film material is mixed and studies, the method that the object of the present invention is to provide a kind of c-BN of realization film n type to mix.At first utilize ion beam assisted depositing to realize high-quality c-BN depositing of thin film, the mode that adopts energetic ion to inject then is injected into c-BN film inside with the S ion, eliminates damage and activator impurity by thermal annealing, realizes the n type of c-BN film is mixed.Usually the ion of monoergic is Gaussian Profile in target material, divides for three steps the S ion of different-energy was injected in the c-BN film among the present invention, thereby realizes the even distribution of impurity S in the c-BN film.This method is utilized energetic ion injection device commonly used on the semiconductor production line on the basis that does not change existing filming equipment, realized that the n type of c-BN mixes, and has advantages such as cost is low, method is easy, use is extensive, portability is good.
The technical scheme that technical solution problem of the present invention is adopted is:
1) adopt ion beam assisted depositing on substrate, to deposit preparation c-BN film;
2) mode that adopts energetic ion to inject is injected into c-BN film inside with the S ion;
3) adopt thermal annealing to eliminate damage and activator impurity, thereby realize the n type of c-BN film is mixed.
Wherein, be that 001 silicon single crystal is as described substrate, with the sputtering target of B target as described c-BN thin film deposition with the crystal orientation
Further, the device of deposition c-BN film is a double-ion beam assistant depositing system, and its background vacuum pressure is 1 * 10
-5Pa, energy and beam current density that Kaufman main ion source of system disposition and the auxilliary ion source of Kaufman, two ion sources can the independent regulation ion beams.
Further, the underlayer temperature during deposition c-BN film is 200～600 ℃, and working gas pressure is 1.0～5.0 * 10
-2Pa.
Further, Ar is adopted in Kaufman main ion source
+Ion, its ion energy are 1200～1500eV, and beam current density is respectively 200～400 μ A/cm
2The auxilliary ion source of Kaufman adopts Ar
+And N
2 +Hybrid ionic, its ion energy are 300～500eV, and beam current density is respectively 60～90 μ A/cm
2, Ar
+: N
2The line ratio be 1: 1.
Further, the ion energy when S injects the c-BN film is 50～100keV, and ion dose is 5 * 10
14Cm
-2
Further, wherein thermal annealing is vacuum annealing, and annealing temperature is 700～900 ℃, and annealing time is 30～90 minutes.
Further, it is that the S ion that branch three goes on foot different-energy is injected into the c-BN film that ion injects, thereby realizes the even distribution of impurity S in the c-BN film.
Utilization is carried out the method that the S ion injects to the c-BN film of ion beam assisted depositing preparation, has realized that the n type of c-BN film mixes.Because the different-energy ion injects degree of depth difference, the method that the different-energy ion that the present invention adopts injects successively can realize the even distribution of impurity S at the c-BN film.Compare with the synchronous growth doping and the diffusion of impurities doping of former c-BN film, advantages such as this method does not have specific (special) requirements to c-BN growth for Thin Film equipment, and the degree of depth with dopant dose and doping can accurately be controlled, cost is low, method is easy, use is extensive, portability is good.The room temperature resistivity that the S ion injects back c-BN film obviously reduces (4 magnitudes of resistivity decreased), lays a good foundation for realizing c-BN base high temperature, high frequency, high-power electronic device.
For further specifying feature of the present invention and technical scheme, the present invention is done a detailed description below in conjunction with application example:
Description of drawings
Fig. 1 is after utilizing three kinds of energy S ions of TRIM simulation to inject the c-BN films according to the embodiment of the invention, the concentration profile of impurity S in the c-BN film;
Fig. 2 is according to Auger electron spectroscopy (AES) figure behind the S injection c-BN film of embodiment of the invention preparation;
Fig. 3 is a Fourier transform infrared spectroscopy of injecting c-BN film front and back on the Si substrate according to the S ion of embodiment of the invention preparation;
Fig. 4 concerns with variation of temperature for the resistance according to the S doping c-BN film of embodiment of the invention preparation.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
Growth technique:
1) the used equipment of growth is the ion beam assisted depositing system, comprises settling chamber, vacuum system, substrate heating and temperature-controlling system, sample rotary system, ion source control system etc.;
2) with high-purity B target as sputtering target;
3) the sample room background vacuum pressure is 1 * 10
-5Pa;
4) at first deposit the c-BN film, main ion source (Ar
+Ion beam) process conditions are: beam current density J
1Be 360 μ A/cm
2, ion energy U
1Be 1500eV; Assisting ion source (Ar
++ N
2 +Ion beam mixing) process conditions are: beam current density J
2Be 80 μ A/cm
2, ion energy U
2Be 300eV, Ar
+: N
2 +The line ratio be 1: 1, the operating pressure between depositional stage is 2.0 * 10
-2Pa, film thickness h are 120nm;
5) then the c-BN film sample is taken out, move to and carry out the injection of multistep ion in the energetic ion implanter process chamber, its process conditions are: operating pressure is 4 * 10
-4Pa injects S energy of ions E and is respectively 50,80 and 100keV, and Dui Ying ion dose Q is respectively 1.3 * 10 with it
14, 0.8 * 10
14, 2.9 * 10
14Cm
-2
6) inject the damage that causes for eliminating, the sample that ion is injected carries out vacuum annealing, annealing temperature T
ABe 900 ℃, annealing time t
ABe 60min;
7) after annealing finishes, when treating that furnace temperature is reduced to room temperature, take out sample.
Growth result:
According to above-mentioned process conditions, on Si (001) substrate, deposited the c-BN film, and injected the S ion of different-energy by ion, realized that the n type of c-BN film mixes.Fig. 1 has provided the concentration profile of the S of impurity in the present embodiment in the c-BN film that utilizes TRIM simulation, and the result shows that the method that adopts different-energy ion (50,80 and 100keV) to inject successively can realize the even distribution of impurity S at the c-BN film.The Auger electron spectroscopy (Fig. 2) of c-BN film also demonstrated the existence of impurity S element really after the S ion injected.The Fourier transform infrared spectroscopy (Fig. 3) of c-BN film showed before ion injected, cube phase content of this sample is 92%, after injecting the S ion, the FTIR spectrum of c-BN film does not have significant change, the component and the structure that show ion injection back c-BN film still remain unchanged, and promptly ion injects less to the damage of film.The measurement result of Hall effect and resistivity shows that S doping back c-BN film is the n type, and its room temperature resistivity drops to 3 * 102 Ω cm from 5 * 106 Ω cm, i.e. 4 magnitudes of its room temperature resistivity decline.S doping c-BN film resistor discloses the semiconductor impurities conductive characteristic of this sample with variation of temperature relation (Fig. 4), and the impurity activation energy that obtains S is 0.32eV.
So far invention has been described in conjunction with the preferred embodiments.Should be appreciated that those skilled in the art can carry out various other change, replacement and interpolations under the situation that does not break away from the spirit and scope of the present invention.Therefore, scope of the present invention is not limited to above-mentioned specific embodiment, and should be limited by claims.
Claims (7)
1. the cubic boron nitride film n type method of mixing is characterized in that this method comprises:
1) adopt ion beam assisted depositing on substrate, to deposit the preparation cubic boron nitride film;
2) mode that adopts energetic ion to inject is injected into cubic boron nitride film inside with sulphion, and the ion energy when sulphion injects cubic boron nitride film is 50～100keV, and ion dose is 0.8 * 10
14Cm
-2, 1.3 * 10
14Cm
-2Or 2.9 * 10
14Cm
-2
3) adopt thermal annealing to eliminate damage and activator impurity, thereby the n type that realizes the cubic boron nitride film mix.
2. the method that cubic boron nitride film n type according to claim 1 mixes is characterized in that, is that 001 silicon single crystal is as described substrate, with the sputtering target of boron target as described cubic boron nitride film deposition with the crystal orientation.
3. the method that cubic boron nitride film n type according to claim 1 mixes is characterized in that the device of described deposition cubic boron nitride film is a double-ion beam assistant depositing system, and its background vacuum pressure is 1 * 10
-5Pascal, energy and beam current density that Kaufman main ion source of system disposition and the auxilliary ion source of Kaufman, two ion sources can the independent regulation ion beams.
4. the method that cubic boron nitride film n type according to claim 1 mixes is characterized in that, the underlayer temperature during described deposition cubic boron nitride film is 200～600 ℃, and working gas pressure is 1.0～5.0 * 10
-2Pascal.
5. the method that cubic boron nitride film n type according to claim 3 mixes is characterized in that, Ar is adopted in described Kaufman main ion source
+Ion, its ion energy are 1200～1500eV, and beam current density is 200～400 μ A/cm
2
6. the method that cubic boron nitride film n type according to claim 3 mixes is characterized in that, the auxilliary ion source of described Kaufman adopts Ar
+And N2
+Hybrid ionic, its ion energy are 300～500eV, and beam current density is 60～90 μ A/cm
2, Ar
+: N
2 +The line ratio be 1: 1.
7. the method that cubic boron nitride film n type according to claim 1 mixes is characterized in that described thermal annealing is vacuum annealing, and annealing temperature is 700～900 ℃, and annealing time is 30～90 minutes.
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| CN2007101777830A CN101441997B (en) | 2007-11-21 | 2007-11-21 | N type doping method for cubic boron nitride film |
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| CN2007101777830A CN101441997B (en) | 2007-11-21 | 2007-11-21 | N type doping method for cubic boron nitride film |
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| CN101441997B true CN101441997B (en) | 2011-08-10 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4316385A (en) * | 1980-06-18 | 1982-02-23 | General Electric Company | Fingerprinting crystals |
| CN1917131A (en) * | 2005-08-18 | 2007-02-21 | 中国科学院半导体研究所 | Filament of neutralization cathode in Kaufman ion source, and method |
-
2007
- 2007-11-21 CN CN2007101777830A patent/CN101441997B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4316385A (en) * | 1980-06-18 | 1982-02-23 | General Electric Company | Fingerprinting crystals |
| CN1917131A (en) * | 2005-08-18 | 2007-02-21 | 中国科学院半导体研究所 | Filament of neutralization cathode in Kaufman ion source, and method |
Non-Patent Citations (4)
| Title |
|---|
| Y.Yamada-Takamura et al..ion implantation effects on the structure and nanomechanicalproperties of vapor deposited cubic boron nitride films.J. Vac. Sci.Technol. B20 3.2002,20(3),936-939. |
| Y.Yamada-Takamura et al..ion implantation effects on the structure and nanomechanicalproperties of vapor deposited cubic boron nitride films.J. Vac. Sci.Technol. B20 3.2002,20(3),936-939. * |
| 蔡志海等.辅助镀膜离子源及立方氮化硼薄膜的制备研究.装甲兵工程学院学报17 1.2003,17(1),18-21. |
| 蔡志海等.辅助镀膜离子源及立方氮化硼薄膜的制备研究.装甲兵工程学院学报17 1.2003,17(1),18-21. * |
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