CN101717913B - N-type nano-diamond film and preparation method - Google Patents
N-type nano-diamond film and preparation method Download PDFInfo
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- CN101717913B CN101717913B CN2009101553063A CN200910155306A CN101717913B CN 101717913 B CN101717913 B CN 101717913B CN 2009101553063 A CN2009101553063 A CN 2009101553063A CN 200910155306 A CN200910155306 A CN 200910155306A CN 101717913 B CN101717913 B CN 101717913B
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- 239000002113 nanodiamond Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 45
- 150000002500 ions Chemical class 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- -1 phosphonium ions Chemical class 0.000 claims abstract description 29
- 238000000137 annealing Methods 0.000 claims abstract description 25
- 238000002347 injection Methods 0.000 claims abstract description 20
- 239000007924 injection Substances 0.000 claims abstract description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000005468 ion implantation Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000002513 implantation Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000006213 oxygenation reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 abstract description 46
- 239000010432 diamond Substances 0.000 abstract description 46
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 10
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 117
- 238000012360 testing method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000005355 Hall effect Effects 0.000 description 10
- 238000005498 polishing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides an n-type nano-diamond film and a preparation method. The preparation method comprises the following steps: injecting donor impurity ions into a nano-diamond film by adopting an ion injection method; and performing vacuum annealing on the film to obtain the n-type nano-diamond film. The method uses the ion injection method to finish the step of doping, so that the phosphonium ions or oxonium ions of which the injected dose is 1,014 to 1,016 cm-2 are doped to nano-diamond crystal grains and crystal boundaries, and the defect that impurities are centralized in the crystal boundaries but cannot enter diamond crystal grains in the processes of chemical vapor deposition and doping is avoided; and after the vacuum annealing at the temperature of between 700 and 1,000 DEG C, the n-type diamond film which has lower resistivity and higher Hall mobility is obtained. Therefore, the n-type nano-diamond film has very important scientific significance and engineering value for the application of the film in the field of semiconductor devices, field emission displays, electrochemistry and the like.
Description
(1) technical field
The present invention relates to a kind of n type nano-diamond film and preparation method thereof.
(2) background technology
Diamond has the wide physicals with the high excellence of carrier mobility in forbidden band, compares electronic materials such as silicon, and it can use in high temperature, high radiation and abominable chemical environment.But diamond does not obtain to use in microelectronics industry at present, and key reason is the n type diamond thin that is difficult to the preparation low-resistivity, waits antetype device thereby be difficult to make the pn knot.Success prepares the n type diamond thin of high conductivity, realizes the application of diamond in microelectronics industry, possibly cause the revolution of electronic industry, has extremely important theory and using value.
For many years, numerous investigators help obtaining adamantine impurity element of low-resistivity n type and adulterating method from Theoretical Calculation and searching experimentally.Main impurity element has nitrogen, phosphorus, sulphur, lithium etc.; Through in process of growth or adopt ion injection method that various impurity are incorporated in single-crystal diamond or the microcrystalline diamond thin film (diamond grain size in the film is a micron order); But all do not obtain good effect; Diamond thin specific conductivity after the doping is low, and electronic mobility is low, is difficult to as electron device.
In recent years, along with the diamond thin Development of Preparation Technology, nano-diamond film has prepared success.Nano-diamond film has excellent physicals, and high like hardness, frictional coefficient is little, and an emission threshold value is low etc.The specific conductivity (～10 of nano-diamond film
-6(Ω cm)
-1) than high 3～7 one magnitude of microcrystalline diamond thin film, but it is still crossed low being difficult to and is applied in the electronic industry owing to specific conductivity.In nano-diamond film, mix the donor impurity element, prepare the n type nano-diamond film of high conductivity, have crucial scientific meaning and construction value realizing its application in fields such as semiconducter device, field-emitter display, electrochemistry.
Characteristics such as the microstructure of nano-diamond film and microcrystalline diamond thin film have bigger difference, and the former is that nano-diamond crystal grain is embedded in the composite structure in the amorphous carbon crystal boundary, has diamond grain size less than 100nm, and the crystal boundary ratio is big; The latter's diamond grain size is at micron order, and the crystal boundary ratio is much smaller than nano-diamond film.As everyone knows, when the size of material during, can have special physical propertiess such as the not available small-size effect of block materials, quantum effect in nanometer scale.Therefore, in Nano diamond crystal grain, mix the donor impurity element and (can discharge electronics and the impurity that produces conduction electrons and form positive center is called donor impurity.Referring to " semiconductor physics " P47, the Electronic Industry Press, Liu Enke, Zhu Bingsheng, Luo Pusheng writes, 2008), its conductivity is compared with same adulterated microcrystalline diamond thin film, possibly have bigger difference; Crystal boundary in the nano-diamond film can become conductive channel in addition.Therefore, in nano-diamond film, mix the donor impurity element, be expected to obtain the n type diamond thin of high conductivity, but domestic and international at present research in this respect is less.
In the chemical vapor deposition processes of nano-diamond film, mix nitrogen abroad, systematically studied the microstructure and the conductivity of nitrogen-doped nanometer diamond thin.The result shows that nitrogen is not the suitable doped source of the high Hall mobility of preparation high conductivity n type nano-diamond film.Nitrogen trends towards preferentially occupying the crystal boundary position in the film rather than gets in the Nano diamond crystal grain, and promptly nitrogen is difficult in and mixes diamond lattice in the chemical vapor deposition processes; Because nitrogen is the deep-level impurity in the diamond, its room temperature intensity of activation in diamond is 1.7eV, and it is difficult to diamond under the room temperature provides n type electricity to lead required electronics.Therefore, the electricity in the nitrogen-doped nanometer diamond thin is led and is mainly come from the film electricity of crystal boundary and lead, and that Nano diamond crystal grain is led contribution to the electricity in the film is little.This electrically conducting manner makes film have specific conductivity and carrier concentration is high, but the very low n type conductive features of carrier mobility.Low carrier mobility makes the depletion layer that is difficult to form rectification and amplifying device needs in the nitrogen-doped nanometer diamond thin, is difficult to the making of electron device, has greatly limited its application on electronic industry.Therefore, improve the conductive capability of nanocrystal and crystal boundary simultaneously, the n type nano-diamond film of the high Hall mobility of preparation high conductivity, significant to realizing the application of nano-diamond film on electronic industry.
(3) summary of the invention
The n type nano-diamond film and the preparation method that the purpose of this invention is to provide the high Hall mobility of a kind of high conductivity.
The technical scheme that the present invention adopts is:
A kind of preparation method of n type nano-diamond film comprises: (1) prepares nano-diamond film on monocrystalline substrate; (2) adopt ion injection method, in nano-diamond film, inject the donor impurity ion; (3), promptly get said n type nano-diamond film with the film vacuum annealing after ion implantation.The present invention uses ion injection method to accomplish the doping step; The donor impurity ion is incorporated in Nano diamond crystal grain and the crystal boundary; Improve the conductive capability of Nano diamond crystal grain and crystal boundary simultaneously; Avoided that impurity concentrates on crystal boundary and can not be incorporated into the shortcoming in the Nano diamond crystal grain in chemical vapour deposition doping process, and carried out vacuum annealing, obtained the n type nano-diamond film that resistivity is lower, the Hall mobility is higher; Said donor impurity ion can be used for mixing the ion of diamond thin for this area routine, like phosphonium ion, oxonium ion, sulfonium ion etc.
Said nano-diamond film can prepare according to this area ordinary method; Adopt the chemical vapor deposition (CVD) method on monocrystalline substrate, to prepare nano-diamond film among the present invention; Can adopt the conventional chemical vapor deposition apparatus to carry out, prepare nano-diamond film thickness usually at 1～10 μ m.
Preferably; Step (1) concrete grammar is following: adopting chemical vapor depsotition equipment, is carbon source with acetone, adopts hydrogen bubbling mode that acetone is brought in the reaction chamber; 600～700 ℃ of temperature of reaction, 5～6 hours reaction times, prepare the nano-diamond film that thickness is 3～4 μ m.
Said donor impurity ion implantation dosage is 10
14～10
16Cm
-2, the injection energy is 90～100keV.
Said vacuum annealing temperature is 700～1000 ℃.
Preferably, said donor impurity ion is phosphorus or oxygen, and implantation dosage is 10
14～10
16Cm
-2, the injection energy is 90～100keV; Vacuum annealing temperature is 700～1000 ℃.
A kind of n type nano-diamond film obtains by injecting the donor impurity ion in the nano-diamond film, it is characterized in that said donor impurity ion is present in the Nano diamond crystal grain and amorphous carbon crystal boundary of nano-diamond film simultaneously; And Nano diamond crystal grain and crystal boundary are that film provides n type electricity to lead.
Preferably, said donor impurity ion is a phosphonium ion.Said n type is mixed the phosphorus nano-diamond film and prepared by following method: (1) adopts chemical Vapor deposition process on monocrystalline substrate, to prepare nano-diamond film; (2) adopt ion injection method, in thickness is the nano-diamond film of 3～4 μ m, inject phosphonium ion, the phosphonium ion implantation dosage is 10
14～10
16Cm
-2, the injection energy is 90～100keV; (3), promptly get said n type and mix the phosphorus nano-diamond film with 700～1000 ℃ of vacuum annealings of the film after ion implantation.
Preferably, said donor impurity ion is an oxonium ion.The oxygen-doped nano-diamond film of said n type is prepared by following method: (1) adopts chemical Vapor deposition process on monocrystalline substrate, to prepare nano-diamond film; (2) adopt ion injection method, in thickness is the nano-diamond film of 3～4 μ m, inject oxonium ion, the oxonium ion implantation dosage is 10
14～10
16Cm
-2, the injection energy is 90～100keV; (3), promptly get the oxygen-doped nano-diamond film of said n type with 700～1000 ℃ of vacuum annealings of the film after ion implantation.
Above-described arbitrary n type nano-diamond film is characterized in that: the concentration of said donor impurity ion in film is 10
18～10
20Cm
-3
Beneficial effect of the present invention is mainly reflected in: (1) method is simple, easy handling; (2) adopt ion injection method can the donor impurity ion be incorporated in Nano diamond crystal grain and the crystal boundary simultaneously, make Nano diamond crystal grain and crystal boundary all to the contribution to some extent of film conduction; Avoided that impurity concentrates on crystal boundary and can not enter into diamond crystals in chemical vapour deposition doping process, promptly Nano diamond crystal grain not have the shortcoming contributed to the film conduction; (3) the n type nano-diamond film resistivity for preparing is low, the Hall mobility high, has crucial scientific meaning and construction value to realizing its application in fields such as semiconducter device, field-emitter display, electrochemistry.
(4) description of drawings
Fig. 1 injects field emission scanning electron microscope (FESEM) photo of nano-diamond film for phosphonium ion;
Fig. 2 injects high-resolution-ration transmission electric-lens (HRTEM) photo of nano-diamond film for phosphonium ion;
Fig. 3 is 10 for the phosphonium ion implantation dosage
15Cm
-2, the Raman spectrum of the nano-diamond film after 900 ℃ of vacuum annealings;
Fig. 4 injects the distribution plan of each element of diamond thin along the depth of film direction for phosphonium ion;
Fig. 5 injects field emission scanning electron microscope (FESEM) photo of nano-diamond film for oxonium ion;
Fig. 6 injects high-resolution-ration transmission electric-lens (HRTEM) photo of nano-diamond film for oxonium ion;
Fig. 7 is 10 for the oxonium ion implantation dosage
14Cm
-2, the ultraviolet Raman spectrum of the nano-diamond film after 900 ℃ of vacuum annealings;
Fig. 8 obtains the O1s center energy level spectrogram that oxonium ion injects nano-diamond film for adopting the XPS test.
(5) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
With nano-diamond powder polishing monocrystalline silicon piece, the polishing time is half a hour approximately.After the silicon chip of polishing cleans through ultrasonic machine, as the substrate of nano-diamond film growth.Adopt hot-wire chemical gas-phase deposition method (chemical vapor depsotition equipment is available from Shanghai Jiaoyou Diamond Coating Co., Ltd.); With acetone is carbon source; Adopt hydrogen bubbling mode that acetone is brought in the reaction chamber; Reaction chamber temperature is controlled at 600～700 ℃, and preparation time is 5～6 hours, prepares the nano-diamond film that thickness is 3～4 μ m.
Adopt the 100keV isotron, the injection energy is 90keV, and implantation dosage is 10 in nano-diamond film
15Cm
-2Phosphonium ion, and 900 ℃ of vacuum annealings 30 minutes.Film after the annealing uses the vitriol oil and ydrogen peroxide 50 (1: 1 volume ratio) mixing solutions to clean 5 minutes, to remove surperficial non-diamond phase with the acetone surface again.Be arranged in the thick metal Ti electrode (1 * 1mm of foursquare 500nm with four of the sputters on film of SPC-350 multi-target magnetic control sputtering appearance
2), then on electrode with vacuum plating unit evaporation metal Au (thick about 500nm), then under the Ar gas shiled 450 ℃ annealed 20 minutes.Adopt the surface topography of field emission scanning electron microscope viewing film, adopt the microstructure of high-resolution-ration transmission electric-lens (HRTEM) viewing film; The excitaton source of employing wavelength 325nm carries out the Raman spectroscopic analysis to the diamond thin of different injection conditions and annealing conditions.(H is C) along the concentration distribution of film thickness direction to adopt sims (IMS CAMECA) to analyze phosphorus and other elements.Adopt Accent HL5500 Hall System instrument, the Hall effect value of sample under the test room temperature.
Fig. 1 is made up of nano level diamond crystals for field emission scanning electron microscope (FESEM) photo of phosphonium ion injection nano-diamond film, visible film; Fig. 2 is high-resolution-ration transmission electric-lens (HRTEM) photo of film; Can find out that diameter is that the diamond crystals (black) of 3～5nm is embedded in the amorphous carbon phase (light gray), shows the composite structure that nano-diamond film is made up of Nano diamond crystal grain and amorphous carbon crystal boundary.Raman spectrum can be analyzed the composition in the diamond thin delicately.The employing wavelength is that the Raman spectrum of 325nm is analyzed thin film composition, and is as shown in Figure 3.Can find out, occur 1332cm in the spectrogram
-1The diamond characteristic peak, show to have the diamond phase in the film; At 1560cm
-1Also can be observed unordered sp
2The graphite peaks of key is explained film mainly by diamond mutually and unordered graphite phase composite, and is consistent with the Raman characteristic spectrogram of common nano-diamond film.The trace elements of second ion mass spectroscopy (SIMS) in can analysed film in order to confirm that phosphonium ion has been incorporated in the film, tested the SIMS spectrogram of sample.Phosphorus the distribution in nano-diamond film of Fig. 4 for adopting the SIMS test to obtain can find out that phosphonium ion is incorporated in the nano-diamond film.The concentration of phosphonium ion in film is about 10
19Cm
-3, and the concentration of phosphonium ion in film descends with the increase of depth of film gradually.
The Hall effect is to detect the strong instrument of the conductivity of film, and the test of Hall effect can obtain resistivity, carrier mobility, carrier concentration and the Hall coefficient of film; When wherein the Hall coefficient was negative, the conduction type that film is described was the n type.To the phosphonium ion implantation dosage is 10
15Cm
-2, and carry out the Hall effect at the nano-diamond film of 700～1000 ℃ of vacuum annealings after 30 minutes and test, the conduction type of gained film is the n type.Representative data is that the resistivity of 900 ℃ of films after the annealing is 10.92 Ω cm, and the Hall mobility is 143cm
2V
-1s
-1, the Hall coefficient is-391m
2/ c, the conduction type that film is described is the n type, and has higher carrier mobility.As a comparison, the Hall effect test data of the nano-diamond film of nitrating in the chemical gas phase process of bibliographical information is 2 * 10
-4m
2V
-1s
-1, peak is 5m
2V
-1s
-1Can find out that this preparation method increases substantially the n type Hall mobility of nano-diamond film.
Embodiment 2:
Adopt nano-diamond powder polishing monocrystalline silicon piece, the polishing time is half a hour approximately.After the silicon chip of polishing cleans through ultrasonic machine, as the substrate of nano-diamond film growth.Adopt hot-wire chemical gas-phase deposition method (chemical vapor depsotition equipment is available from Shanghai Jiaoyou Diamond Coating Co., Ltd.); With acetone is carbon source; Adopt hydrogen bubbling mode that acetone is brought in the reaction chamber; Reaction chamber temperature is controlled at 600～700 ℃, and preparation time is 5～6 hours, prepares the nano-diamond film that thickness is 3～4 μ m.
Adopt the 100keV isotron, the injection energy is 90keV, and implantation dosage is 10 in nano-diamond film
14Cm
-2Oxonium ion (O
+, generally use O in the document of this area
+The expression oxonium ion, in ion implantation technology, an electronics generally peeling this atom off makes it become positively charged ion; Different with common ion notion chemically), and 900 ℃ of vacuum annealings 30 minutes, the film after the annealing used the vitriol oil and ydrogen peroxide 50 (1: 1 volume ratio) mixing solutions to clean 5 minutes, to remove surperficial non-diamond phase with the acetone surface again.Be arranged in the thick metal Ti electrode (1 * 1mm of foursquare 500nm with four of the sputters on film of SPC-350 multi-target magnetic control sputtering appearance
2), then on electrode with vacuum plating unit evaporation metal Au (thick about 500nm), then under the Ar gas shiled 450 ℃ annealed 20 minutes.Adopt the surface topography of field emission scanning electron microscope viewing film, adopt the microstructure of high-resolution-ration transmission electric-lens (HRTEM) viewing film; The excitaton source of employing wavelength 224nm carries out the Raman spectroscopic analysis to the diamond thin of different injection conditions and annealing conditions.Adopt x-ray photoelectron spectroscopy (VG ESCALAB 220I-XL) to analyze the one-tenth bonded state in the Nano diamond, adopt Accent HL5500 Hall System instrument, the Hall effect value of sample under the test room temperature.
Fig. 4 is made up of nano level diamond crystals for field emission scanning electron microscope (FESEM) photo of oxonium ion injection nano-diamond film, visible film; Fig. 5 injects high-resolution-ration transmission electric-lens (HRTEM) photo of nano-diamond film for oxonium ion; Can find out that diameter is that the diamond crystals (black) of 3～5nm is embedded in the amorphous carbon phase (light gray), shows the composite structure that nano-diamond film is made up of Nano diamond crystal grain and amorphous carbon crystal boundary.Fig. 6 is 10 for the oxonium ion implantation dosage
14Cm
-2, the ultraviolet Raman spectrum of the nano-diamond film after 900 ℃ of vacuum annealings.Can find out, in the spectrogram at 1332cm
-1There is sharp-pointed diamond characteristic peak in the place, at 1560cm
-1The place is unordered sp
2The graphite peaks of key, show exist in the film diamond mutually with unordered graphite mutually, consistent with common nano-diamond film.Fig. 8 tests the O1s center energy level spectrogram of the nano-diamond film that obtains for adopting x-ray photoelectron spectroscopy XPS, and near the peak in the spectrogram 532eV is the characteristic peak of C-O key, shows that oxygen has been incorporated in the nano-diamond film really; The concentration of oxonium ion in film is approximately 10
18Cm
-3
Adopt the electric property of Hall effect testing film, test result shows that oxonium ion injects and the resistivity of annealing rear film is 25.19 Ω cm, and the Hall mobility is 11.4cm
2V
-1s
-1, the Hall coefficient is-71.8m
2/ C, the film that shows gained is n type electricity leads.As a comparison, the Hall effect test data of the nano-diamond film of nitrating in the chemical gas phase process of bibliographical information is 2 * 10
-4m
2V
-1s
-1, peak is 5m
2V
-1s
-1Can find out that the sample that adopts this method to prepare has better n type conductivity.
Embodiment 3:
Adopt nano-diamond powder polishing monocrystalline silicon piece, the polishing time is half a hour approximately.After the silicon chip of polishing cleans through ultrasonic machine, as the substrate of nano-diamond film growth.Adopt hot-wire chemical gas-phase deposition method (chemical vapor depsotition equipment is available from Shanghai Jiaoyou Diamond Coating Co., Ltd.); With acetone is carbon source; Adopt hydrogen bubbling mode that acetone is brought in the reaction chamber; Reaction chamber temperature is controlled at 600～700 ℃, and preparation time is 5～6 hours, prepares the nano-diamond film that thickness is 3～4 μ m.
Adopt the 100keV isotron, implantation dosage is 10 in nano-diamond film
15Cm
-2Sulfonium ion (S
+, generally use S in the document of this area
+The expression sulfonium ion; In ion implantation technology, an electronics generally peeling this atom off makes it become positively charged ion, and is different with common ion notion chemically); And 900 ℃ of vacuum annealings 30 minutes; Film after the annealing uses the vitriol oil and ydrogen peroxide 50 (1: 1 volume ratio) mixing solutions to clean 5 minutes, to remove surperficial non-diamond phase with the acetone surface again.Be arranged in the thick metal Ti electrode (1 * 1mm of foursquare 500nm with four of the sputters on film of SPC-350 multi-target magnetic control sputtering appearance
2), then on electrode with vacuum plating unit evaporation metal Au (thick about 500nm), then under the Ar gas shiled 450 ℃ annealed 20 minutes.Adopt Accent HL5500 Hall System instrument, the Hall effect value of sample under the test room temperature.
Hall effect test result shows that sulfonium ion injects and the resistivity of annealing rear film is 6.51 Ω cm, and the Hall mobility is 0.90cm
2V
-1s
-1, the Hall coefficient is-0.147m
2/ C, the film that shows gained is n type electricity leads.
Claims (4)
1. the preparation method of a n type nano-diamond film, comprising: (1) prepares nano-diamond film on monocrystalline substrate; (2) adopt ion injection method, in nano-diamond film, inject the donor impurity ion; Said donor impurity ion is phosphorus or oxygen, and implantation dosage is 10
14～10
16Cm
-2, the injection energy is 90～100keV; (3) with the film vacuum annealing after ion implantation, annealing temperature is 700～1000 ℃, promptly gets said n type nano-diamond film.
2. the method for claim 1; The preparation method who it is characterized in that said step (1) is following: adopt chemical vapor depsotition equipment; With acetone is carbon source; Adopt hydrogen bubbling mode that acetone is brought in the reaction chamber, 600～700 ℃ of temperature of reaction, 5～6 hours reaction times, prepare the nano-diamond film that thickness is 3～4 μ m.
3. n type nano-diamond film that adopts the method for claim 1 preparation; Obtain by injecting the donor impurity ion in the nano-diamond film, it is characterized in that said donor impurity ion is present in the Nano diamond crystal grain and amorphous carbon crystal boundary of nano-diamond film simultaneously; Nano diamond crystal grain and crystal boundary are that film provides n type electricity to lead; Said donor impurity ion is phosphonium ion or oxonium ion.
4. n type nano-diamond film as claimed in claim 3 is characterized in that: the concentration of said donor impurity ion in film is 10
18～10
20Cm
-3
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|---|---|---|---|
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| CN101956178A (en) * | 2010-09-28 | 2011-01-26 | 浙江工业大学 | Boron-doped nanocrystalline diamond film and preparation method thereof |
| CN103060771B (en) * | 2012-12-31 | 2016-04-06 | 内蒙古科技大学 | Single crystal type polycrystal nano-diamond composite film and preparation method |
| US10211049B2 (en) * | 2015-08-07 | 2019-02-19 | North Carolina State University | Synthesis and processing of pure and NV nanodiamonds and other nanostructures |
| CN108531883B (en) * | 2018-03-23 | 2020-06-09 | 浙江工业大学 | High-mobility n-type ultrathin nano-diamond film and preparation method thereof |
| CN108660429B (en) * | 2018-03-23 | 2020-06-23 | 浙江工业大学 | Grain-close-packed n-type nano-diamond film and preparation method thereof |
| CN108660432B (en) * | 2018-03-23 | 2020-06-09 | 浙江工业大学 | High-mobility n-type nano-diamond film with crystal grain close-packed structure and preparation method thereof |
| CN108838052B (en) * | 2018-07-12 | 2021-08-24 | 郑州人造金刚石及制品工程技术研究中心有限公司 | Orthodontic stainless steel material plated with nano carbon crystal film on surface and preparation method thereof |
| CN110600366B (en) * | 2019-09-20 | 2021-06-18 | 西安交通大学 | (100) Crystal orientation diamond n-channel junction field effect transistor and preparation method thereof |
| CN111155071B (en) * | 2019-12-25 | 2022-06-21 | 浙江工业大学 | Sulfur ion injection nano diamond-graphene composite film electrode and preparation method thereof |
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| CN103060767B (en) * | 2012-12-31 | 2015-05-27 | 浙江工业大学 | High-mobility n-type nano-diamond film and preparation method thereof |
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