CN1028772C - Method and apparatus for vapor deposition of diamond - Google Patents
Method and apparatus for vapor deposition of diamond Download PDFInfo
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- CN1028772C CN1028772C CN 88101737 CN88101737A CN1028772C CN 1028772 C CN1028772 C CN 1028772C CN 88101737 CN88101737 CN 88101737 CN 88101737 A CN88101737 A CN 88101737A CN 1028772 C CN1028772 C CN 1028772C
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Abstract
A method for vapor deposition of diamond by effecting an arc discharge while feeding a discharge gas between an anode and a cathode of a thermal plasma chemical vapor deposition device, radicalizing a gaseous carbon compound by feeding the gaseous carbon compound into a generated plasma jet, and permitting the radicalized plasma jet to impinge on a substrate to be treated, whereby a film of diamond is formed on the substrate.
Description
The invention relates to a kind of method and device of vapor deposition of diamond.Or rather, the present invention relates to a kind of high efficiency method and device of even vapor deposition of diamond, particularly a kind of diamond film that under the high deposition rate of film, obtains with adequate thickness, good membranes quality.
Diamond is a kind of allotropic substance of carbon, and it demonstrates diamond lattic structure, has high Mohs' hardness, and its value is 10; Compare with other material, it has superior thermal conductance value, and its value is 2000W/MK.
The carbon of diamond-like also is known, and it is the allotropic substance of element of the same race.Though it is an amorphous, transparent and insulation.This product also demonstrates high thermal conductance value and hardness value, and is adamantine although its value is lower than, and these factors make this material use in many ways becomes possibility.
Or rather, the prominent part of this material is to utilize its high thermal conductance value as the substrate material that semiconductor integrated circuit is installed; Utilize the coating of its high hardness value as instrument etc.Also have, the carbon of diamond-like when on the surface of coated at titanium mesh, the oscillating plate of available speaker.
Especially adamantine thermal conductance value is 2000W/MK, and this is equivalent to four times of high copper, and it also has good hardness and insulating property, therefore, is the desirable material of semiconductor element scatterer, and as the material of circuit substrate.And in very wide wavelength region, diamond has good light transitivity, so it still is a kind of good optical material.In addition, because adamantine frequency band very wide (be 5.45ev), and be a kind of semi-conductor with high hall mobility, be used for high effect device so work as it, high temperature crystal pipe for example, high speed transistors etc. are just noticeable.
Vapour phase processes for the carbon of man-made diamond or diamond-like has proposed and has studied such method, for example chemical vapor deposition method (CVD method), ion plating, ionization vapor deposition method, sputtering method or the like.In the middle of them, what demonstrate the most possible property of batch process is the CVD method.According to the exciting method of reaction gas, this method can be categorized as heated filament utmost point CVD method, microwave plasma CVD technique, and electronics quickens CVD method or the like.
Or rather, for having the method for high-quality vapour phase diamond synthesis, known for example heated filament utmost point method (S.Matsumoto et al, Japan, J.Appl.Phys of chemical vapor deposition method (CVD method), 21(1981) L183), microwave plasma CVD technique (M.Kamo et al., J.Cryst, Growth.62(1983) 642), electronics quickens CVD method (A.Sawbe et al., Appl.Phys Lett.46(1985) 1467 or the like.
Yet according to these preparation methods, the deposition rate of diamond film is low to moderate n μ m/h or lower, although and used cheap device and raw material because productivity is low, cost is also higher, therefore, sees not practical from practical angle.Also have, high-frequency thermal plasma CVD method (Society of Applied Physics, Spring Season Lecture Mareh 1987) shortcoming is also arranged, promptly under 30 μ m or higher thickness, the surface is by greying, so,, may prepare thick film though can reach the high film deposition rate of 1 μ m/min.The speed of the thermal plasma that high frequency produces is very low, therefore, substrate must be placed on the place that contacts with thermal plasma, so the temperature of substrate surface raises, thereby can prepare thick film.In addition, owing to formed the very big thermal plasma of volume, so the flow velocity of thermal plasma is very low, can not provide sufficiently high speed of cooling, thereby can not obtain the layer of even diamond film the water-cooled substrate.
Therefore, though existing multiple sedimentation can utilize, and all can realize depositing diamond by each described method, but the deposition rate with high-quality film only is 1 μ/h or lower, its quality can only be surveyed adamantine crest according to raman spectroscopy and measure.In addition, with regard to the carbon of diamond-like, deposition speed is very low, only is about 10 μ m/h, and this is a problem concerning producing in batches.
In sum, need develop a kind of sedimentation of high rate deposition film.
As mentioned above, with regard to the sedimentation of diamond film, proposed and studied diverse ways, but in the CVD method that but makes in the best, adamantine deposition rate only is 1 μ m/h or lower, therefore, the CVD method of exploitation high rate deposition film must await realizing.
Therefore, the objective of the invention is to eliminate the shortcoming of above-mentioned prior art, a kind of method and device that is used for having at vapor deposition of diamond on the substrate and under than higher film deposition rate enough thickness and good film quality is provided.
From following explanation, can see other purpose of the present invention and advantage.
According to the present invention, a kind of method of vapor deposition of diamond is provided, this method comprises the steps:
Carry out arc-over when between the anode and cathode of a thermal plasma CVD (Chemical Vapor Deposition) apparatus, feeding discharge gas,
Make the gaseous carbon compound free radicalization by in the plasma jet that generates, feeding gas, and
Make the pending substrate of plasma jet collision of free radicalization, thereby on substrate, formed one deck diamond film.
According to the present invention, a kind of adamantine vapor deposition method also is provided, this method comprises the steps:
A kind of hydrogen-containing gas and one of a kind of gaseous carbon compound feeding are had in the thermal plasma generating unit of anode and negative electrode;
Make the gas free radicalization by interelectrode direct current arc discharge;
Inject the thermal plasma that is plasma jet to a underpressure chamber; And
By making thermal plasma stream collision refrigerative substrate quenching plasma jet, thus on substrate deposit one deck diamond film.
According to the present invention, a kind of method of vapor deposition of diamond further is provided, this method comprises the steps:
Inwall by a plurality of nozzles of in closed system, opening form an a kind of polar electric pole and and its opposite polarity a plurality of electrodes between apply direct current, carry out arc-over, thereby free radicalization or activation hydrogen and the gas that contains the gaseous state carbon compound form a kind of thermal plasma;
Inject plasma jet to the underpressure chamber;
By making thermal plasma stream collision refrigerative substrate, the quenching plasma jet, thereby on substrate deposit one deck diamond film.
According to the present invention, a kind of formation plasma apparatus also is provided, this device is a kind of device that forms plasma jet, comprise that one is furnished with discharge gas pneumatic tube, unstripped gas or the pneumatic tube of conveying solid substance particulate gas and the obturator of direct supply and electric wire, and the nozzle that wherein has the injection plasma jet of unlatching, this device is characterised in that, wherein a plurality of nozzles are opened, the inwall of each nozzle has formed has same polar electrode respectively, and a plurality of electrodes with opposite polarity are arranged in the closed system, so that they are facing to the inwall of each nozzle.
According to the present invention, a kind of method of vapor deposition of diamond also is provided, this method comprises the steps:
Gas is passed in the thermal plasma generating unit with anode and negative electrode of blowpipe form;
Make the gas free radicalization by between electrode, carrying out the direct current arc discharge, to form a kind of thermal plasma;
Penetrate the thermal plasma that is plasma jet by nozzle at the blowpipe tip.
In plasma jet, spray into cold gas, so that plasma body quenching and form a kind of active nonequilibrium plasma that contains the free radical product that forms by the carbon compound free radicalization that joins in the plasma jet at least and have very high number of free radical; And,
Substrate is contacted with nonequilibrium plasma, thus on substrate deposit one deck diamond film.
According to the present invention, a kind of method of vapor deposition of diamond further is provided, this method is to have negative electrode and anodic direct current plasma blowpipe carries out arc-over by one, meanwhile, between negative and positive the two poles of the earth, feed discharge gas, and the plasma body that radiation forms on pending substrate, to form one deck diamond film thereon, this method comprises at least two plasma body blowpipes of use, in a blowpipe, a kind of gas of higher sparking voltage is made plasma body, to make plasma body than the reactive gaseous state carbon compound of low discharge voltage in the remaining blowpipe, and make these two kinds of plasma bodys collide substrate, thereby form one deck diamond film with pattern.
According to the present invention, a kind of method of vapor deposition of diamond also is provided, this method comprises the steps:
Use a plurality of plasma body blowpipes,
A plurality of plasma jets are collided mutually, in these plasma jets, carbon source is made plasma body to form diamond film.
According to the present invention, a kind of method of vapor deposition of diamond further is provided, this method comprises the steps:
A kind of discharge gas and a kind of raw material that contains a gaseous carbon compound at least that forms by arc-over made plasma body;
Inject as the thermal plasma that is plasma jet, and
Make the plasma quenching with deposit one deck diamond film on substrate, wherein make the unsettled part material at least of arc-over join the center that plasma jet causes end, and not by the arc-over part.
With reference to following description of drawings, will understand the present invention better, wherein:
Fig. 1 has illustrated the principle of thermal plasma CVD method implemented according to the invention.
Fig. 2 illustrative one be used to implement thermal plasma CVD device of the present invention;
Fig. 3 has illustrated an embodiment of thermal plasma vapor phase synthesis;
Fig. 4 has illustrated another embodiment of thermal plasma vapor phase synthesis;
Fig. 5 is the temperature variation of the hydrogen molecule decomposition reaction equilibrium constant.
Fig. 6 is the sectional view of a thermal plasma flow generating apparatus of the present invention;
Fig. 7 is the fish-eye view of a thermal plasma generating unit of the present invention;
Fig. 8 is the sectional view of another thermal plasma flow generating apparatus of the present invention;
Fig. 9 is the legend that adopts the vapour phase synthesizer of plasma jet generating unit of the present invention.
Figure 10 (a) has illustrated DC plasma body vapour phase synthetic principle of the present invention, Figure 10 (b), and Figure 10 (c) is the sectional view of plasma body blowpipe;
Figure 11 (a) and (b) be respectively figure and photo has shown the state according to the DC plasma jet of embodiment of the present invention;
Figure 12 (a) and (b) be respectively figure and photo has shown the state according to the DC plasma body vapour phase synthetic plasma jet of another embodiment of the invention;
Figure 13 illustrative according to plasma CVD method adamantine formation on substrate.
Figure 14 illustrative be used to implement thermal plasma CVD device of the present invention;
Figure 15 has illustrated plasma jet CVD ratio juris of the present invention:
Figure 16 is the overall pattern that is used to implement plasma jet CVD subtraction unit of the present invention;
Figure 17 has shown the crystalline structure according to diamond film of the present invention;
Figure 18 has shown the crystalline structure of diamond film according to another embodiment of the present invention;
Figure 19 has illustrated the principle of plasma jet jet apparatus of the present invention;
Figure 20 is a scanning electron photomicrograph, has shown the surface of diamond film;
Figure 21 is a scanning electron photomicrograph, has shown the surface and the cross section of diamond film;
Figure 22 has shown the X-ray diffraction result of diamond film;
Figure 23 has shown the Raman spectrum of diamond film;
Figure 24 has shown air cooling direct current plasma stream vapour phase synthesizer of the present invention;
Figure 25 is an electron scanning micrograph, has shown the surface of diamond film;
Figure 26 is an electron scanning micrograph, has shown the surface and the cross section of diamond film;
Figure 27 has shown the X-ray diffraction result of diamond film;
Figure 28 has shown the raman spectrum of diamond film; And
Figure 29 has shown the emmission spectrum according to DC plasma jet of the present invention and traditional microwave plasma.
According to the present invention,, diamond is deposited on the pending substrate by using a kind of thermal plasma CVD device (being used for the synthesize ceramic fine powder).
Fig. 1 has shown the thermal plasma ratio juris that is used for CVD of the present invention, wherein, when discharge gas 3 passes through between anode 1 and the negative electrode 2, applies voltage and carries out arc-over, and be 5000 ℃ or higher arc plasma thereby produce temperature.
By being arranged on the inlet on the anode 1, unstripped gas 4 is passed into arc plasma and forms part, be heated to high temperature rapidly and be activated, thereby form highdensity free radical, volumetric expansion simultaneously to be sprayed, with ultra-high speed plasma jet 6 by nozzle 5.
Adopt aforesaid method, attempted synthetic high melting compound powder, for example silicon carbide (SiC) or silicon nitride (Si
3N
4).More particularly, test, wherein concerning producing SiC, silane (SiH
4) and methane (CH
4) join in the arc plasma as unstripped gas; For producing SiN, add SiN
4And ammonia (NH
3), activate and by making free radical reaction prepare powder.
The present invention has developed this method, is intended to react thereby carried out effective CVD on substrate before the life-span, short free radical disappeared, thus film forming by making the pending substrate 7 of plasma jet 6 collisions.In addition, in the process of on substrate, reacting, apply the optical excitation that the ultraviolet radiation that produces in arc-over and the plasma collision process causes and the energy that obtains.
So, the present invention has produced far above the density by high-temperature electric arc (being higher than 5000 ℃) the resultant free radical of activatory prior art, simultaneously, carry free radical and free radical reaction is taken place to pending substrate, thereby effectively carry out the diamond deposit by the energy that obtains from above-mentioned optical excitation and collision.
In process according to second embodiment diamond synthesis of CVD method of the present invention, a kind of carbon compound (as methane, acetylene, alcohol, propyl alcohol, methylamine, ethylene dichloride etc.) is decomposed with activation with the gas mixture of hydrogen, and (promptly 400～1500 ℃ of diamonds are deposited on the substrate under the temperature of suitable vapor deposition of diamond.Adamantine synthetic in, consider that active specy (as hydrogen atom and alkyl) plays an important role in vapour phase, in order to improve adamantine deposition rate, can prepare the plasma body of highdensity such active specy and be transported on the substrate surface.
The plasma body that has higher activity and high dissociation degree about molecule, known a kind of thermal plasma, wherein different chemical species, for example ion, electronics, the neutrophil granule temperature in plasma body is substantially the same, and its temperature is 5000K or higher.Fig. 5 has shown the dissociation reaction (H of hydrogen molecule
2=2H) equilibrium constant is with variation of temperature, but when 500K as can be seen, almost all hydrogen molecules are dissociated into hydrogen atom.Yet when the thermal plasma under this temperature contacted with substrate, the temperature of substrate rose De Taigao, was difficult to diamond synthesis.
Fig. 3 is illustrating according to direct-current discharge thermal plasma stream (VI) method diamond synthesis of the present invention.
When carrying hydrogen-containing gas 17 and gaseous carbide 18, between anode 15 and negative electrode 16, apply volts DS and carry out electric arc 19 discharges, at this moment, gas is heated suddenly between narrow electrode, and becoming temperature around nozzle 20 is 5000 ℃ or higher thermal plasma.In this case,, make volumetric expansion, thereby make thermal plasma become a kind of ultransonic plasma jet 21 and inject chamber 22 by nozzle 20 because temperature rises suddenly.
Figure 29 has shown the emmission spectrum according to DC plasma jet of the present invention and traditional microwave plasma body.Article two, spectral line is got accurate in H
2The peak.In microwave plasma, determine hydrogen molecule live width and strong emission peak (＜480nm, 560～620nm).But in the DC plasma jet, because hydrogen molecule is launched very weak.These results mean, compare with traditional microwave plasma, and the dissociation degree of hydrogen is very high for the DC plasma jet.
By making plasma jet 21 collision substrates 24 quenching plasma jets (wherein efficiently cooling off), active specy, for example short-life hydrogen reacts on substrate before disappearance, thereby synthesizes diamond film 25.
In addition, in on-chip reaction, the kinetic energy that is applied is to obtain by intensive ultraviolet optical excitation and ultrasonic particle encounter that arc-over produces.
Therefore, compare with the method for prior art, the efficient that chemical reaction can be much higher is carried out in the present invention, therefore can be under high deposition speed diamond synthesis.
In the present invention, any carbon compound all can be used as unstripped gas, but preferably uses a kind of hydrocarbon, or contain oxygen in a kind of molecule, the hydrocarbon or the halohydrocarbon of nitrogen or halogen.
Except the unstripped gas of hydrogen unstripped gas and carbon compound, mix the stability that a kind of rare gas element (as argon, nitrogen etc.) can improve arc-over.In this case,, therefrom can obtain advantage, can improve the homogeneity on film surface though may reduce the deposition rate of film.
Also have, by mixing a spot of a kind of oxidizing gas, for example oxygen, water, hydrogen peroxide, carbon monoxide etc. can be strengthened the effect of the carbon of etching non-diamond.
Because hydrogen is as discharge gas, and it as shown in Figure 5, has high ionizing potential to be difficult to discharge, so electrode materials preferably should have high thermotolerance.The tungsten that wherein has a kind of rare earth oxide (as lanthanum trioxide, yttrium oxide, cerium oxide etc.) to add is a kind of good electrode materials.In addition, in order to prevent the impurity of carrying under one's arms in the electrode, the most handy highly purified carbon dioxide process carbon electrode.
According to the 3rd embodiment of the present invention, because the thermal plasma that forms is heated to about 5000 ℃, it expands suddenly and penetrates by nozzle.Because nozzle bore is narrow, only is 1～2mm, therefore penetrates the area that collides the cooling substrate and be about 25mm from a nozzle
2In the present invention, plasma jet penetrates by a plurality of nozzles, and therefore, film deposit area can enlarge.
Also have, the homogeneity of film can be improved by following method in the deposition process: a kind of rare gas element (for example hydrogen or helium) is sneaked among the unstripped gas of hydrogen discharge gas or carbon compound or the two, perhaps can be with a kind of oxidizing gas (as oxygen, hydrogen peroxide or water) sneak into, to remove the carbon of the non-diamond in the film that is mixed in etching formation.
Plasma generator comprises an obturator as shown in Figure 6, the negative electrode 27 that its inside has formed anode 26 and supported by insulation component, or the like.Discharge gas pneumatic tube 28 communicates with obturator, the communicate inside of on electrode 26 a plurality of nozzles 31 of setting of the pneumatic tube 29 of unstripped gas or conveying solid substance particulate gas.Apply volts DS by lead 30 to electrode, between electrode, producing the successive electrical discharge arc, thereby make discharge gas and unstripped gas activation, form pyritous plasma jet 33.
As shown in Figure 9, for according to chemical vapour deposition diamond of the present invention, the thermal plasma generating unit is arranged in the underpressure chamber 37, and chamber 37 is furnished with water-cooled substrate holder 36, is used for supporting the substrate 35 relative with nozzle 31.As shown in Figure 7, the aperture of four nozzles 31 respectively is 2mm, and nozzle center is 5mm apart from minimum, substrate 35(20mm
2) place nozzle 31 following 10mm.Room pressure reduces to 100 torrs, and hydrogen is added by discharge gas pneumatic tube 28 with the flow velocity of 1000SCCm, and methane is introduced nozzle 31 with the flow velocity of 100SCCm from unstripped gas pneumatic tube 29.Apply the direct current of 2KW between electrode, by quenching, thickness is about 80 μ m to the plasma jet 33 that arc-over produces, area is about 4cm thereby formed by colliding substrate 1 hour continuously
2Diamond film.The area of this film is 16 times of the area that obtains during only with a nozzle, and as shown in Figure 8, the defeated pipe 29 of unstripped gas also can be in the unlatching of the outside of nozzle 31, so that gas is blown into plasma jet.
According to the present invention, in the adamantine method of direct current plasma jet chemical deposition, high-speed film forming is possible, and the film forming area can improve significantly, thereby has realized the improvement of cost and production.
In the superincumbent example, adopt plasma jet to carry out adamantine chemical vapour deposition, but also can with the powder that contains a kind of inorganics or metallics with a kind of gas (as hydrogen) by unstripped gas be loaded with liquid or carefully admittedly the pneumatic tube of particulate gas be transported to the inside of nozzle 31, and with plasma jet fusion inorganics or metallics, thereby on substrate, form one deck plasma spray coating.
As shown in Figure 8, by unstripped gas carry liquid or carefully admittedly the pneumatic tube 29(of particulate gas open in the outside of nozzle 31) fine particle of inorganics or metallics can and be blown in the plasma jet by conveying such as hydrogen.With regard to metallics, can use refractory metal, superalloy, sintering metal etc.With regard to inorganics, can use superconducting material, pottery, graphite, glass of Y-Ba-Cu-O system, Bi-Sr-Ca-O system etc.About inorganics, a kind of powder is such as Y-Ba-Cu-O system superconductivity ceramics powder, by the input of gas pneumatic tube, is about 100 μ m to form a layer thickness, area is 4cm
2Plasma spraying.Through actual measurement, this plasma sprayed coating demonstrates supraconductivity when liquid nitrogen temperature, and resistance value is zero under 88.5K absolute temperature.
According to the 4th embodiment of the present invention, replace the method that the substrate that is cooled by collision makes the thermal plasma quenching, and adopt the method that in plasma jet, is blown into (air cooling method).
According to the present invention, this method can produce the irrelevant nonequilibrium plasma of a kind of and substrate, because by forcing plasma jet to mix with gas under room temperature to cause thermal plasma moment to be cooled.Therefore, can form under the adamantine temperature, by pending material is remained in the nonequilibrium plasma, diamond synthesis at a high speed on substrate.Recommending the temperature of substrate is 800 ℃～1300 ℃.
Figure 10 (a) has shown that wherein 38 is negative electrodes according to the principle of gas cooling DC plasma jet CVD method diamond synthesis of the present invention, the 39th, and anode, the 40th, discharge gas, the 41st, nozzle, the 42nd, plasma jet, the 43rd, cold gas spout, the 44th, cold gas, the 45th, substrate, the 46th, diamond film, the 47th, arc power, the 48th, electric arc, the 49th, nonequilibrium plasma.Can say with regard to plasma body blowpipe 50, can adopt the blowpipe of the unitary electrode shown in Figure 10 (b), or the multi-electrode blowpipe shown in Figure 10 (c).
When feeding contains the discharge gas 40 of hydrogen and gaseous carbon compound, between negative electrode 38 and anode 39, apply volts DS to excite electric arc 48 discharges, thereby discharge gas is heated up suddenly, and becoming a kind of is 5000 ℃ or higher thermal plasma in nozzle 41 surrounding temperatures.In this operating process,, spray thereby make thermal plasma become a kind of ultrasonic plasma jet 42 and pass through nozzle 41 because temperature raises suddenly and causes volumetric expansion.
Hydrogen blows to plasma jet 42 as cold gas 44, forces and mixes, and makes the thermal plasma quenching whereby, produces nonequilibrium plasma 49.By substrate 45 is placed non-equilibrium plasma 49, active specy (as short-life hydrogen atom) reacts with substrate before disappearance, grows diamond film 46 in its surface.
Figure 11 (a) and (b) and Figure 12 (a) (b) show as or do not have cold gas by the time plasma jet situation.With regard to Figure 12 (a) and (b), when with air cooling but the time, obviously the length of plasma jet will extremely be lacked so that the thermal plasma quenching.
Therefore the present invention compares with the direct current plasma stream CVD method of obstructed overcooling air-flow, and is irrelevant with substrate because thermal plasma stream can be by quenching, therefore to the type of substrate used without limits, and makes the diamond can be with high-speed rapid growth on any substrate.
In the present invention, any hydrocarbon all can be used as unstripped gas, but preferably uses hydrocarbon or the halohydrocarbon that contains oxygen, nitrogen and halogen in the molecule.
Except hydrogen, to mix with a kind of raw material discharge gas of carbon compound by making a kind of rare gas element (as hydrogen, helium), the stability of arc-over can improve.In this case,, obtained benefit, promptly improved the homogeneity of face although thin-film deposition speed may reduce.
Also have,,, also can improve the effect of removing non-diamond carbon with etching as water, hydrogen peroxide and carbon monoxide by mixing small amounts gas.
Because used the hydrogen with high ionization gesture as discharge gas, electrode materials preferably has high thermotolerance.The tungsten that wherein has a rare earth oxide (as lanthanum trioxide, ytterbium oxide, selenium oxide etc.) adding is a kind of fabulous electrode materials.In addition, for preventing the electrode impurity of carrying under one's arms, preferably use the high purity carbon electrode.
As previously mentioned, the method of prior art diamond synthesis film does not satisfy industrialization demands, according to the 5th embodiment of the present invention, founded a kind of novel method of utilizing the principle diamond synthesis film of plasma flame injection, industrialization diamond synthesis film becomes possibility on the substrate thereby make.
Yet in this method, for instance, the gaseous mixture of hydrogen and gaseous state carbon compound such as methane is as gas, and adopts the vapour deposition of thermal plasma stream CVD device forming one deck diamond film, but problem produced, this be because, for example:
(1) hydrogen discharge voltage is high.
(2) because methane cracking produces heat and volumetric expansion.
(3) cause carbon and electrode reaction etc. by the methane cracking that is attached on the flame spray apparatus.
Substrate temperature and plasma flow change thus, can not synthesize even diamond film.
Figure 13 illustrates above-mentioned thermal plasma CVD ratio juris, and this method applies a voltage by direct supply 56 and excites arc-over, feeds discharge gas (H simultaneously between anode 53 and negative electrode 54
2+ CH
4) 55, produce the arc plasma of 5000 ℃ or higher temperature.
Feed unstripped gas 55 that arc plasma in the plasma body blowpipe forms part and sharply be heated to high temperature and be activated, and produce the high-density free radical, thus volumetric expansion and spray from nozzle with supersonic velocity as plasma jet 58.
According to this method, make the pending substrate of plasma jet 58 collisions, before short-life free radical disappears, realize high-level efficiency CVD reaction on the substrate, form diamond film 60 thus.The substrate 59 that is used for above-mentioned purpose places a water-cooled substrate holder 61, is added into water coolant 62 in the water-cooled substrate holder 61 and is cooled to temperature and is for example 400～1500 ℃, preferably 800～1300 ℃.
Yet, as mentioned above, although diamond film effectively vapour deposition to substrate,, cause the problem that can not synthesize even diamond film thus owing to above-mentioned reason still can not obtain stable plasma jet.On the contrary, according to the present invention, as shown in figure 14, prepare two plasma torch 64 and 65, H
2Gas (or the hydrogen that is equipped with by traditional law system and the gas mixture of indifferent gas) is introduced a blowpipe, and methane (CH
4) gas (or gas mixture of methane and rare gas element such as Ar) introduces another blowpipe.Between anode 66,67 and negative electrode 68,69, impose voltage respectively by direct supply 70 and 71 and excite arc-over, eject plasma jet 72 and 73 thus.On the substrate 75 that places on the water cooling substrate holder, these plasma jet deposits become uniform diamond film 76.
Consider by allowing a large amount of plasma bodys to collide mutually, make carbon compound in plasma jet, make plasma body and quenching compound, formed a large amount of fine diamond nucleis.Therefore, can prepare the level and smooth diamond film of excellent in uniform according to a sixth embodiment of the invention, this with only prepare with plasma body blowpipe, only grow a small amount of diamond nuclei and the diamond film air spots cunning that obtains is different.
Figure 15 has illustrated that another produces the plasma jet blowpipe and is installed in thermal plasma Apparatus for video CD principle.Wherein 78 is anodes, the 79th, and negative electrode, the 80th, discharge gas or contain the discharge gas of unstripped gas, the 81st, cold gas or contain the cold gas of unstripped gas, the 82nd, electric arc, the 83rd, nozzle, the 84th, plasma jet, the 85th, vacuum chamber, the 86th, substrate holder, the 87th, substrate, the 88th, diamond film.
Figure 16 implements device overall pattern of the present invention, and 89 is first plasma torch among the figure, and 90 is second plasma torch, 91 and 92 is arc powers of supplying with each blowpipe, 93,94th, and the chilled water unit of each blowpipe, the 95th, the substrate controller, the 96th, the blowpipe controller, the 97th, pumped vacuum systems, the 98th, play the shape gas cylinder, the 99th, under meter, the 100th, discharge gas or contain the discharge gas pneumatic tube of unstripped gas, the 101st, unstripped gas and (or) the cold gas pneumatic tube, the 102nd, the cold gas jet pipe.
5cm
2Silicon substrate 87 be placed in 100mm places below the blowpipe 87, be evacuated down to 1 * 10 torr with rotor pump after, under the system pressure of 3KW discharge power and 100 torrs, with discharge gas H
2With 50SCCm, unstripped gas CH
4Join in the blowpipe 89 with 500SCCm.Meanwhile, be under the condition of 1KW at discharge power, the discharge gas of 20SLM and the unstripped gas of 100SCCm input blowpipe 90.And at distance substrate 35cm and become 60 jiaos blowpipe place film forming with substrate.Last 1 hour.Find with X-ray diffraction and with Raman spectroscopy, made the film that demonstrates the diamond crest.Figure 17 shows the diamond film with the preparation of two plasma body blowpipes according to the present invention, and this film thickness is 35 μ m, and wherein film forming speed is 100 μ m/hr per hour.Figure 18 shows the diamond film of only making with a plasma body blowpipe by control methods.According to the present invention, the diamond film with smooth and homogeneous surface can be to make at a high speed.
In above-mentioned example, hydrogen is input to respectively plasma body blowpipe 89 and 90 from unstripped gas pneumatic tube 101 from discharge tracheae 100, methane gas, but also can in discharge gas pneumatic tube 100, not only import hydrogen but also import methane gas, or the neutralization of unstripped gas pneumatic tube (or) both imported cold gas H in the cold gas pneumatic tube 101
2Import methane gas again.Also can carry out various distortion, for example, will discharge gas and unstripped gas only are input in one of them blowpipe.And only discharge gas is input in the another one blowpipe or the like.Its essence is exactly to launch a large amount of plasma jets and in plasma jet carbon source is made plasma body to form diamond on substrate.Also have, for deposition speed, the angle of a plurality of plasma jets preferably should be perpendicular to substrate; But also can pre-determine a best angle on request.
As above-mentioned a plurality of plasma jets, mentioned with direct current arc discharge generation direct-current plasma, but also can use various a plurality of plasma bodys, the RF plasma jet of high frequency discharge for example, photoelectric arc plasma jet with the laser photoelectricity arc discharge produces carries out the plasma jet of microwave plasma stream alternating current discharge generation etc. with microwave discharge method.Atmosphere as for producing plasma body is preferably under the reduced atmosphere, but also can be used to form diamond under the situation of normal atmosphere or supercharging.The also available diamond synthesis powder of this in addition method.
According to the 6th embodiment of the present invention, with direct current plasma stream CVD method, can go out diamond film and its smooth surface is even with high speed production, so the range of application of coating can expand very wide scope to, and radiator element or diamond circuit substrate that semiconductor device is used can be finished easily.
The diamond film epitaxial growth method of the 7th embodiment of the present invention, comprise the raw material of carbonaceous sources is injected to etc. exsomatize by the quenching thermal plasma in and growing diamond.
In the diamond film method, hydrogen is usually as discharge gas, and any carbon compound all can be used as the unstripped gas of carbon source, but contains a kind of hydrocarbon or the organism of elements such as O, N, halogen in the most handy hydrocarbon polymer or the molecule.Rare gas elementes such as a kind of Ar of elephant, He also can be mixed in discharge gas or the unstripped gas.In this case, the stability of plasma body can further improve, but the film deposition rate has reduced.Also have, in order to strengthen the etch effect of non-diamond carbon (as amorphous carbon), a spot of a kind of oxidizing gas such as O
2, H
2O, CO etc. also can mix in unstripped gas.
In addition, by minimum gas is resembled B
2H
2, NH
3, PH
3Also can obtain semiconductor diamond Deng mixing in unstripped gas or these minimum gas being imported separately in the plasma jet.
Unstripped gas is input to the initiation end center of plasma jet without the arc-over part.Preferably use following plasma jet jet apparatus of the present invention for this reason.When plasma jet jet apparatus of the present invention is used for high temperature superconducting oxide (Ba-Y-Ca-O system, when plasma flame Bi-Sr-Ca-Cu-O system etc.) sprays, the fine powder of superconducting oxide with a kind of carrier gas be input to as shown in figure 19 109 in, fusing and on matrix, form one deck effective film in plasma jet.Certainly also can use plasma atmosphere, oxidizing atmosphere, oxygen atmosphere, air atmosphere etc. in this case.
Plasma jet jet apparatus of the present invention has the transfer port 109 of the unstripped gas gas of raw material powder (or contain) as shown in figure 19, and it stretches and a nozzle 108 that is positioned at nozzle 106 centers of outer electrode 104 arranged along the central axis of interior electrode 103.Electric arc 113 discharges between outer electrode 104 and electrode 103, but unstripped gas (or raw material powder gas) 109 will not contact with electric arc 113.Like this, do not hinder the uniform electric arc 113 of formation.In addition, because unstripped gas 109(or contain the gas of raw material powder) be discharged into plasma jet 107 and cause the end centres, make that the plasma distribution that forms is even in plasma jet 107, for vapour deposition or thermal plasma, utilize this plasma jet to help the formation and the growth of deposit product, can generate a uniform and smooth film thus.
Note, by using adamantine this device of generation and a kind of raw material except that diamond as substrate, can be at its surperficial synthesised polycrystalline diamond.
Figure 19 has illustrated the principle of utilizing apparatus of the present invention to generate diamond film.
This device is applicable to unstripped gas is input in the plasma jet so that be input to unstripped gas in the plasma jet equably by the nozzle that is contained in cloudy plate center, can improve the homogeneity of film thickness thus, or under the situation that when unstripped gas is carbon compound, can restrain the generation of graphite.Among the figure.The 103rd, negative electrode, the 104th, anode, the 105th, discharge gas, the 106th, nozzle, the 107th, plasma jet, the 108th, unstripped gas ejiction opening, the 109th, unstripped gas, the 110th, substrate, the 111st, diamond film, the 112nd, arc power, the 113rd, electric arc.
When hydrogen as discharge gas from 20 liters/minute flow velocity and methane gas as unstripped gas during with 0.2 liter of/minute flow rate, between anode and cathode, apply volts DS 90V, electric current 10A, be used for laser-arc 113 discharge, thereby the discharge gas around nozzle 106 is heated as 5000 ℃ or be higher than 5000 ℃ thermal plasma stream.In this case, cause that volumetric expansion, thermal plasma stream become ultrasonic plasma jet 107 because temperature sharply raises, this ultrasonic plasma jet is by nozzle 106 ejections.Unstripped gas is directly inputted in the plasma jet without discharge portion, thereby is decomposed and activates.Plasma jet collides the back quenching by the molybdenum substrate with 5 * 5 * 0.5mm, and the result generates diamond film, and therefore just obtaining thickness in 1 hour is 200 μ m polycrystalline diamond films.Find during the surface measurements rugosity that Rmax is 10 μ m, comparing with (Rmax is 50 μ m) of the method preparation of importing simultaneously according to unstripped gas and discharge gas has obtained improving greatly.
In this device,, therefore obtain stable discharge owing to do not contain unstripped gas in the electric arc.Also have, owing to, can suppress the generation of graphite in all unstripped gas input plasma jets.
With regard to diamond film, be favourable owing to using hydrogen, only be because of the high ionization gesture may cause the discharge difficulty, have high heat resistance so preferably use, the electrode materials of energy stable discharging.The tungsten that wherein has addings such as lanthanum trioxide, yttrium oxide, cerium oxide is good electrode materials.There is impurity to carry under one's arms for fear of electrode in addition, preferably uses highly purified carbon dioxide process carbon electrode.
It is synthetic that plasma jet jet apparatus of the present invention should be used for foregoing diamond, still, also can be used for other purpose certainly.
Embodiment
The present invention is existing to be described further by the following examples, but is not subjected to the restriction of these embodiment, wherein all umbers and per-cent all by weight, unless outpour especially.
Fig. 2 is used to implement thermal plasma schematic representation of apparatus of the present invention, and the plasma jet generating unit branch shown in Fig. 1 is expressed as plasma body blowpipe 8.
Placed a substrate holder 9 over against plasma body blowpipe 8 in device, substrate holder is a water-cooled, and pending substrate 7 is put thereon.
Also have, this device connects a pumped vacuum systems 10.
Secondly, plasma body blowpipe 8 connects discharge gas pneumatic tube 11, be used for feeding discharge gas between discharge electrode 1 and 2, and unstripped gas pneumatic tube 12, be used for to arc plasma transferring raw material gas.Also provide arc power 13 to provide power supply and grid bias power supply 14 to discharge electrode so that free radical focuses on the pending substrate 7.
Then, as embodiment, handle a 30mm
2Silicon substrate, substrate and plasma body blowpipe 8 spacings keep 300mm.
At first, will install inside with pumped vacuum systems 10 and be evacuated down to 1 * 10
-3Behind the torr, feed hydrogen (H with the 1000SCCM flow velocity by discharge gas pneumatic tube 11
2), add methane gas (CH by raw material pneumatic tube 12 with the 100SCCM flow velocity
4), make indoor vacuum tightness remain on 100 torrs with pumped vacuum systems 10, thereafter, arc power power supply 2KW, bias voltage power supply 300V.
Then, after carrying out thermal plasma CVD, the diamond film thickness that forms in 1 hour is about 10 μ m, shows that with X-ray diffraction and raman spectrum determination and analysis the diamond crest is only arranged.
Compare (its deposition rate is 1 μ m or lower) deposition speed with prior art CVD and will exceed an order of magnitude or higher.
According to the present invention, owing to can produce the free radical of very high-density, compare with prior art, the speed that forms diamond film is wanted a high order of magnitude, thereby can satisfy the requirement to the large-scale integrated circuit substrate.
Water-cooled substrate holder 23 can horizontal or vertically move, and the distance of nozzle and substrate also can change.
5mm
2, the silicon chip that 0.2mm is thick is fixed on the substrate holder 23, and chamber 22 vacuumizes 2 * 10
-3Behind the torr, as shown in Figure 3, hydrogen is at 1kg/cm
2Pressure under with 20 liters/minute flow velocity, and as the methane gas of unstripped gas 18 at 1kg/cm
2Pressure under the flow rate of dividing with 40cc/ between electrode, flow through, chamber 22 internal pressures remain on 100 torrs simultaneously.From a Constant Electric Current arc power, the constant current of 10A and keeps about 5 minutes until voltage constant between electrode.At this moment voltage is 72V.
Water-cooled substrate holder 23 is gently near nozzle 20, and the fixed distance between nozzle and substrate is at 5mm, and diamond synthesis lasts for the moment little in this state.By electron scanning micrograph (SEM), X-ray diffraction, the synthetic diamond is estimated in raman spectrum and hardness measurement.
As shown in figure 20, the surface of diamond film is become by the regularly arranged diamond crystal structures that flocks together.The SEM of Figure 21 shows the middle part of diamond film sectional view, the top on the bottom of silicon substrate sectional view and diamond film surface.Therefore can find out and be formed uniformly slightly uneven diamond surface.Figure 22 shows the X-ray diffraction figure of diamond film, and diamond plane surface (111), (220), (331) seem extremely clear, and (331) and (440) still can debate out.Figure 23 has represented the diamond film raman spectrum, still can debate out adamantine intrinsic peak at wave number 1333cm among the figure, can find out easily that also other carbonaceous material of nothing such as graphite occur.
About the HV500 Vickers' hardness, because sample hardness height be difficult to differentiate impression, but through actual measurement, pressure reaches 8000kg/cm
2Or it is higher.By top data as can be known, the synthetic diamond is the high-quality polycrystalline film.And to record thickness be 80 μ m, and the speed of synthetic excellent diamonds is higher than 10 times of prior art 80 μ m/h or higher.
In addition, under this condition, when synthetic 10 hours, the thickness at substrate center position became 1mm, and its peripheral part is 0.6mm.Equally, promptly use X-ray diffraction, Raman spectroscopy still only obtains the diamond crest, does not measure to have graphite.
Embodiment 3(Fig. 4)
With the molybdenum plate of 10 * a 10 * 0.2mm as substrate, as shown in Figure 4, as the hydrogen of discharge gas 17 with 20 liters/minute, hydrogen with 20 liters of/minute feedings, the hydrogen that contains 2% acetone as unstripped gas 18 joins in the plasma jet with 2 liters/minute, under the situation of flame current 20A, voltage 60V, nozzle one substrate spacing 10mm, diamond synthesis one hour.Thickness 60 μ m, and film quality is similar to embodiment 2.
Embodiment 4-9(Fig. 3 and Fig. 4)
In addition, when reaction conditions changes, for example change interelectrode feed gas or gas is input in the thermal plasma stream that forms between the electrode, the diamond film forming speed is summarized in the following table.The quality of the diamond film that obtains and embodiment 2 are approximate.(table is seen the literary composition back)
According to plasma jet CVD method of the present invention, high-quality diamond can be with the speed deposit of 80 μ m/h, and this speed thus, makes cheap adamantine practical application obtain remarkable progress by vapor phase synthesis far above the speed of prior art.When being used for semi-conductive scatterer or circuit substrate, cost is descended and improved performance significantly according to present method synthetic diamond.
Embodiment 10(Figure 24)
Figure 24 has illustrated that wherein 115 is plasma body blowpipes according to the diamond synthesizer of air cooling DC plasma jet CVD method of the invention process, the 116th, and discharge gas pneumatic tube, the 117th, cold gas pneumatic tube, the 114th, arc power, the 118th, blowpipe cooling water pipeline, the 119th, substrate holder, the 120th, substrate, the 121st, vacuum chamber, the 122nd, pumped vacuum systems, the 123rd, blowpipe controller, the 124th, under meter, the 125th, gas storage cylinder, the 126th, the cold gas jet orifice, and 127 are substrate controllers.
The plasma body blowpipe has water-cooling structure, is by wherein adding 2%(weight) tungsten of yttrium oxide makes with negative electrode and anode 38.The position separately and the direction of plasma body blowpipe 115 and substrate holder 119 can be controlled by controller, the result on the large area substrates or have that complexity shows shape and on the material that needs to handle diamond film can increase equably.Although do not illustrate in Figure 24, substrate holder 119 also can be equipped with the well heater that is used for heated substrate or be used to control the water cooling plant of substrate temperature.
Embodiment 11(Figure 24)
The silicon chip that uses 5 * a 5 * 0.2mm is evacuated to 2 * 10 as substrate in the vacuum chamber
-3Torr, as the discharge gas hydrogen at pressure 1kg/cm
2With 20 liters/minute, methane gas is at pressure 1kg/cm down
2Between electrode, flow through down with 80 ml/min flows, hydrogen as cold gas at pressure 1kg/cm
2Flow to keep vacuum chamber pressure with 20 liters/minute down at 200 torrs.By placing four cold gas spouts 126 at 3mm place, blowpipe nozzle below, shown in Figure 24 sprays to plasma jet by cold gas source capsule 117 supply cold gas.Flow through between the electrode of plasma torch 115 by the 10A constant current that Constant Electric Current arc power 114 is supplied with, keeps stablizing until voltage in 5 minutes.At this moment voltage is 65V.By substrate holder 119 slowly being shifted to the nozzle of blowpipe 115, the fixed distance that makes nozzle one substrate face is at 5mm, and film forming is 10 minutes under this condition.According to scanning electron photomicrograph (SEM), X-ray diffraction, prepared diamond is estimated in Raman spectroscopy and hardness measurement.
SEM shown in Figure 25 shows that diamond surface has diamond crystal, their regularly arranged flocking together.
On the other hand, SEM shows among Figure 26, and the middle part is the diamond cross section, and the bottom is the silicon substrate cross section, and top is the diamond film surface, also can find out the even slightly surface of uneven diamond film that formed.
Can find out that also the synthetic diamond is the dense multicrystalline body with clear same shape, thickness is 15 μ m.
Figure 27 shows that diamond film X-ray diffraction figure has a CuK α
1Line, extremely tangible diamond plane surface (111), (220), and (331), and (331) and (400) still can discern.So only measured the diamond spike of cubic system.Figure 28 shows the raman spectrum of diamond film, and can discern from figure also is at wave number 1333cm
-1Intrinsic peak in the diamond at place, and can find out the carbonaceous material that other is arranged, as the crest of graphite.
Through actual measurement, vickers hardness number is identical with the value of natural diamond, and 500 gram loads are about 10000kg/cm down
2
By The above results as can be seen, the synthetic diamond is high-quality polycrystalline film.Can see that also the membrane deposition rate is up to 100 μ m/h.
Embodiment 12(Figure 24)
Under the filming condition of embodiment 11, as substrate, and make the plasma body blowpipe with the platinum plate of 10 * a 10 * 1mm to of the velocity sweeping of platinum plate with 2mm/h, form the diamond film of thick 0.4mm on the platinum substrate.Diamond film is peeled off from substrate, become the diamond plate of 10 * 10 * 0.4mm.
Show under different condition the repeatedly result of diamond synthesis below.(table is seen the literary composition back)
In the above-described embodiment, do not adopt gas cooling:
As substrate, internal vacuum chamber is evacuated to 2 * 10 with the silicon chip of 5 * 5 * 0.2mm
-3Behind the torr, at 1kg/cm
2Pressure under, hydrogen as discharge gas with 2 liters/minute flow rate, at 1kg/cm
2Methane gas flows between electrode with the flow velocity of 400 ml/min under the pressure, thereby vacuum chamber pressure is maintained 100 torrs, pass to the electric current of 10A and keep 5 minutes by Constant Electric Current arc power blowpipe up to voltage constant, this moment, voltage was 6.5V, make the gently close blowpipe of substrate holder 119 among Figure 24, the fixed distance that makes nozzle and substrate has been finished the deposit of film in this state at 15mm, last one hour, and to have obtained thickness be the gem grade diamond film of 60 μ m.
In above-mentioned example, as the method that forms active nonequilibrium plasma by quenching with high free concentration, cooling gas collides the plasma body that sprays from four gas cooling spouts of plasma body in an example shown, but cooling gas also can spray to the plasma body axle center.Also can only face toward plasma jet shower cooling gas towards a direction, distributing with formation temperature maybe to form the number of free radical distribution.
According to the CVD method of gas cooling direct current plasma stream of the present invention, compare with not using gas cooling direct current plasma stream CVD method, but because the thermal plasma quenching, and irrelevant with substrate, so diamond can be grown on any substrate.Need not cool off substrate, the fine diamond can generate with about 100 μ m/ hours high film deposition speed.Widened the range of application of diamond coatings thus greatly.
Pass through vapor phase synthesis, make cheap adamantine practical application greatly before go a step further, and when being used for radiator element or semiconductor circuit substrate, the synthetic diamond will make cost reduce greatly in this way, and performance is improved, so diamond heat sink or be used for semi-conductive diamond circuit substrate and be easy to realize.
Utilize the device shown in Figure 13 (embodiment) and Figure 14 (embodiment 20), the silicon substrate of 10 * 10 * 0.5mm thickness is placed on on the substrate holder of water quench, and by as the plasma torch of electrode diamond film being deposited on the substrate with tungsten.
In device shown in Figure 14, when the mixed gas of introducing hydrogen (20 liters/minute of flow velocitys) and methane (0.2 liter/minute of flow velocity) discharges, central value is that the sparking voltage of 90V fluctuates between ± 20V, and the shape of plasma jet has changed greatly, finishes with regard to deposit in one hour and thickness is the diamond film of 180 μ m.This film has only unique diamond crest when analyzing with X-ray diffraction and raman spectrum.
On the other hand, in the device shown in Figure 14, each is imported respectively when discharging in each blowpipe with the speed of 20 liters/minute (hydrogen) and 0.2 liter/minute (methane gas) when hydrogen and methane gas, the sparking voltage of hydrogen blowpipe is highly stable, its value is 100V ± 2V, the sparking voltage of methane blowpipe is 30V ± 2V, and the dimensionally stable of plasma jet has obtained the uniform diamond film that thickness is about 150 μ m.
As mentioned above, according to the present invention, because hydrogen and carbon compound gas (as methane) are with independent plasma jet input, compare with the method that the gaseous mixture of introducing hydrogen and methane gas discharges, highly stable and high efficiency diamond film can be formed, therefore the requirement of large-scale integrated circuit can be satisfied substrate.Similarly, also can utilize the indirect heat filament according to the present invention, microwave discharge and RF discharge rather than discharge with direct current arc.
Embodiment 22(Figure 19)
A kind of plasma jet CVD device that Figure 19 and Figure 24 illustrative are used in method of the present invention is implemented, 115 is plasma body blowpipes among the figure, the 116th, discharge gas input tube, the 114th, arc power, the 118th, the cooling water pipeline of blowpipe, the 119th, substrate holder, the 120th, the diamond substrate, the 121st, vacuum chamber, the 122nd, pumped vacuum systems, the 123rd, blowpipe controller, the 124th, under meter, the 125th, gas storage cylinder, the 126th, unstripped gas input tube, the 127th, substrate controller.
Plasma body blowpipe 115 is a water-cooling structure, by adding the 2%(treatment) tungsten of yttrium oxide makes with negative electrode and anode.The position of plasma body blowpipe 115 and substrate holder 119 and direction are respectively by controller 124,127 control, they can both move with respect to plasma jet and substrate, thereby even can be at growing diamond film or form diamond film on the material of surface shape complexity equably on the substrate big area.Though do not express in the diagram,, the well heater or the water-cooled body of heated substrate can also be installed in order to control the temperature of substrate.
With II a type 2 * 2 * 0.5mm man-made diamond substrate, take out straight sky to 2 * 10 at vacuum chamber
-3Behind the torr, at 1kg/cm
2Pressure under, hydrogen as discharge gas with 20 liters/minute flow velocity and feed gas methane with 0.1 liter/minute flow rate, can make the pressure of vacuum chamber remain on 120 torrs.
The electric current of 20A feeds blowpipe and keeps 5 minutes up to voltage constant from the Constant Electric Current arc power, and the voltage of this moment is 50V, and when substrate was made substrate at leisure near blowpipe, the spacing stuck-at-5mm of nozzle one substrate, film forming under this state was lasted one hour.
When the diamond of making was analyzed with raman spectrum and hardness measurement, Raman spectroscopy went out unique diamond peak value, and Vickers' hardness equals the hardness of natural diamond, was 10000 when load 500 grams promptly.The diamond thickness is 150 μ m, and rate of film build is 150 μ m/ hours.
Equally, carry out X-ray diffraction, and low energy electron diffraction (LEED) confirms that the single-crystal diamond film is epitaxially grown on the base diamond substrate by Laue method.
Find that in this embodiment the fluctuation of arc voltage is about 10%.Therefore be 20% with the discharge method comparison with voltage fluctuation of (as shown in figure 13) of the gaseous mixture of introducing hydrogen and methane gas, the stability of electric arc has also been improved.
In this embodiment, still the generation of not finding to have graphite.
In addition, under embodiment 22 filming conditions, with the flow velocity of 0.1 ml/min with B
2H
6Sneak in the unstripped gas as impurity gas, film forming need be carried out 10 minutes, and what obtain is a kind ofly to have 10
-2The P-type semiconductor diamond of Ω m resistivity.
(5 * 5 * 0.2mm) as substrate, and it is 2 * 10 that vacuum chamber is vacuumized with silicon chip
-3Behind the torr, at 1kg/cm
2Pressure under, hydrogen discharge gas is with 20 liters/minute flow velocity, methane feed gas makes vacuum chamber pressure maintain 100 torrs with 0.5 liter/minute the flow velocity vacuum chamber of flowing through.
The electric current of 20A is from Constant Electric Current arc power feeding blowpipe and keep about 5 minutes until voltage constant, and this moment, voltage was 50V.Make substrate slowly close blowpipe, nozzle to the fixed distance of substrate is 20mm, carries out film forming in this state, lasts one hour.
Made diamond film X-ray diffraction, raman spectrum and hardness measurement are estimated.As a result, by X-ray diffraction, Raman spectroscopy only has unique diamond crest, and its dimension paper hardness value equates that with the natural diamond hardness value both be about 10000 under 500g load, the diamond thickness is 200 μ m/ hours.
When synthetic diamond film surface roughness is measured, find that Rmax is approximately 10 μ m, this with unstripped gas in to contain the Rmax that obtains after the input of discharge gas be that 50 μ m compare widely and improved.
In this embodiment, the fluctuation of in the process of diamond synthesis, finding arc voltage be 10% with method that the gaseous mixture of introducing hydrogen and methane gas discharges in arc voltage fluctuation be 20% to compare, the stability of electric arc also is improved.
In addition, in this embodiment, the position does not have graphite to produce around the substrate.
As substrate, methane is as the flow velocity input of unstripped gas with 0.2 liter/minute with the molybdenum sheet of 5 * 5 * 0.5mm, and making the voltage on the anodic-cathodic is 90V, and electric current is 10A, under the filming condition of embodiment 26, can obtain similar result.
Figure 19 shows the sectional view of plasma jet jet apparatus, but negative electrode 103 and anode 104 can be symmetrically distributed, and the unstripped gas spout of negative electrode 103 and nozzle 106 can be Polygons (rectangle etc.) or ellipse, but will produce uneven discharge characteristic.Also have, if need can be equipped with on the electrode pectination thread form heat-resistant insulation material, this will not influence discharge, help applying in large area.
With regard to substrate, except that diamond, silica glass, tungsten, molybdenum etc. are not handled the generation that yet can be used for film to the surface.
With regard to discharge atmosphere, be preferably in for the stability of electric arc under the situation of decompression and use discharge atmosphere, but under normal pressure and supercharging situation, also can use.Show the example that diamond film generates in the above-described embodiments, but method also can be used for the diamond synthesis powder.
Equally, as mentioned above, plasma jet jet apparatus of the present invention also can be used for the plasma flame spraying as high-temperature superconductor oxide compounds such as Ba-Y-Cu-O systems.
When utilizing modified version direct current plasma of the present invention stream CVD device to generate diamond film, be approximately with its deposition rate and can synthesize very slick surface, good diamond film in 200 μ m/ hours rapidly.Therefore the range of application of diamond film is expanded widely.
Carry out the epitaxial film growth according to direct current plasma stream CVD method, the epitaxial film thickness that obtains with 150 μ m/ hours high film forming speeds is 150 μ m.
Can obtain to be used for the diamond heat sink and the diamond semiconductor circuit substrate of semiconductor device easily, in addition, can synthesized semiconductor diamond, also can be used for resembling the plasma flame spraying of the inorganics of high temperature superconducting oxide etc.
Embodiment numbers 456789
Feed gas H between electrode
220 H
220 H
220 H
220 H
220 H
220
（l/min） CH
4l CH
3OH0.5 Ar10 CH
4l CH
3Cl0.04 CH
3F0.04
H
201
Join material gas triethylamine 0.1 Ar2 in the jet
（l/min） H
22 H
2O
20.5
Substrate thickness (μ m) Si200 Si200 Mo200 Si200 Si200 Si200
Pressure (holder) 120 120 200 130 120 120
Flame current (A) 10 10 10 10 10 10
Nozzle-substrate spacing 555555
（mm）
High speed production gem grade diamond example
Discharge gas H
220 H
210 H
220 H
220 H
220 H
220
（l/min） Ar10 CH
40.2
CH
40.06 H
2O0.1
Cold gas H
220 H
220 H
220 H
220 H
220 H
220
(l/min) CH
40.5 acetone 2 CH
3Cl0.5 acetone 2
Substrate thickness Si2 Si2 Si2 Si2 Si2 Si2
（mm）
Pressure (holder) 200 200 200 200 200 200
Electric current (A) 10 10 10 10 10 10
Nozzle-substrate 555555
Distance (mm)
(μ m/ hour)
Non-prime diamond example
Comparative example 1234
Discharge gas H
220 H
210 H
220 H
220
（l/min） Ar10 CH
40.5 CH
40.08
CH
40.06 H
2O0.1
Cold gas H
220 H
220 H
220 H
220
（l/min） CH
40.5
Substrate thickness Si2 Si2 Si2 Si2
（mm）
Pressure (holder) 200 200 200 200
Flame current (A) 10 10 10 10
Nozzle-substrate 20 555
Distance (mm)
Film deposition rate 300
(μ m/ hour)
Product does not have substrate fusion decolorizing carbon and does not have
Claims (34)
1, a kind of method of vapor deposition of diamond, this method comprises the steps:
(i) thus carrying out the direct current arc discharge when charging into a kind of discharge gas between the negative electrode of a thermal plasma CVD (Chemical Vapor Deposition) apparatus and at least one anode produces a kind of plasma jet;
(ii) make hydrogen and gaseous carbon compound free radicalization by adding hydrogen and gaseous carbon compound in plasma jet, and
(iii) make the pending substrate of described free radical plasma jet collision, thereby on substrate, form one deck diamond film,
Wherein make its cooling or by toward plasma jet in, being blown into the quenching of cooling gas plasma jet, so that formation contains the active nonequilibrium plasma of high density free radical by the collision substrate.
2, according to the process of claim 1 wherein that the thermal plasma CVD (Chemical Vapor Deposition) apparatus is made up of a direct current plasma blowpipe.
3, in accordance with the method for claim 2, wherein the gaseous state carbon compound is a kind of hydrocarbon, or contains the hydrocarbon of oxygen, nitrogen or halogen in a kind of molecule.
4, according to the method for claim 2, wherein hydrogen-containing gas and gaseous carbide further contain a kind of rare gas element, oxidizing gas or its mixture.
5, according to the method for claim 4, wherein oxidizing gas is oxygen, water, hydrogen peroxide or carbon monoxide.
6, according to the method for claim 2, wherein hydrogen-containing gas and gaseous carbon compound feed between the electrode of thermal plasma generating unit.
7, according to the method for claim 2, wherein hydrogen-containing gas is passed between the electrode of thermal plasma generating unit, and the gas of carbonaceous compound is passed into the plasma jet that sprays between electrode.
8, according to the method for claim 2, wherein by using a carbon dioxide process carbon electrode and a tungsten electrode that contains a kind of rare earth oxide to carry out arc-over as electrode.
9, according to the method for claim 2, wherein said method comprises the steps:
The inwall of the nozzle of a plurality of unlatchings by in closed system, forming a kind of polar electric pole and and and the opposite polarity a plurality of electrodes of nozzle between apply direct current and carry out arc-over;
Make hydrogen and a kind of gas free radicalization that contains the gaseous state carbon compound, form a kind of thermal plasma that contains the dissociates hydrogen atom;
Spray the thermal plasma of the plasma jet that contains the gas atom that dissociates to a underpressure chamber; And
At 400 ℃-1500 ℃, collide on the substrate in cooling by described plasma jet, make the plasma body quenching, thus on substrate deposit one deck diamond film.
10, according to the method for claim 9, wherein gaseous carbon compound is a kind of hydrocarbon, or contains oxygen in a kind of molecule, the hydrocarbon of nitrogen or halogen.
11, according to the method for claim 9, the gas of hydrogen-containing gas or gaseous carbon compound wherein, a kind of rare gas element in containing in addition, a kind of oxidizing gas or mixture.
12, according to the method for claim 9, wherein oxic gas is oxygen, water, hydrogen peroxide or carbon monoxide.
13, according to the method for claim 9, wherein a kind of hydrogen-containing gas and a kind of gaseous state carbon compound are passed between the electrode of thermal plasma generating unit.
14, according to the method for claim 9, wherein a kind of hydrogen-containing gas is passed between the electrode of thermal plasma generating unit, and a kind of gas of carbonaceous compound is passed into the plasma flow that ejects between electrode.
15,, wherein carry out the direct current arc discharge as electrode by the tungsten electrode that uses a carbon dioxide process carbon electrode or contain rare earth oxide according to the method for claim 9.
16, contain hydrogen according to the process of claim 1 wherein in the cold gas.
17, contain gaseous carbon compound at feed gas, cold gas or its in the two according to the process of claim 1 wherein.
18, according to the process of claim 1 wherein that gaseous carbon compound is the hydrocarbon that contains oxygen, nitrogen or halogen in a kind of hydrocarbon or a kind of molecule.
19, contain a kind of rare gas element at feed gas, cold gas or its in the two according to the process of claim 1 wherein.
20,, wherein feed in feed gas from the plasma body that nozzle penetrates or cold gas or this two kinds of gases and contain oxidizing gas according to the method for claim 19.
21, according to the method for claim 20, wherein oxidizing gas is oxygen, water, hydrogen peroxide or carbon monoxide.
22,, wherein carry out the direct current arc discharge as electrode by the metal electrode that uses a carbon dioxide process carbon electrode or contain a rare earth oxide according to the method for claim 20.
23, according to the method for claim 1, wherein the thermal plasma CVD (Chemical Vapor Deposition) apparatus is made up of at least two plasma torch, this method also comprises: in a blowpipe gas of higher sparking voltage is made a kind of plasma body therein, in remaining blowpipe, will make a kind of plasma body than the active gaseous carbon compound of low discharge voltage, and these two kinds of plasma bodys are collided substrate simultaneously with the effusive form, thereby on substrate, form diamond.
24, according to the method for claim 24, the gas that wherein has higher sparking voltage is hydrogen.
25, according to the method for claim 23, wherein gaseous carbide is the hydrocarbon that contains oxygen, nitrogen or halogen in a kind of hydrocarbon or a kind of molecule.
26, according to the adamantine method of the vapor deposition of claim 24, a plurality of plasma jets that wherein a plurality of plasma torch allow to form in the plasma torch collide mutually, form diamond thus to make carbon make plasma body in described plasma jet.
27, according to the method for claim 26, wherein adopt a plurality of plasma torch, carbon compound is made plasma body, a plurality of plasma jets run foul of each other, and make the quenching and being radiated on the substrate in described plasma jet of this plasma body, on substrate, to prepare uniform and smooth diamond film.
28, according to any one described method among claim 1-12 or the 16-23, wherein be the initiation end center that gaseous carbon compound is imported into above-mentioned plasma flow at least, and not by the arc-over part.
29, according to the method for claim 28, the gas that wherein discharges is hydrogen, a kind of rare gas element or its mixture.
30, according to the method for claim 28, wherein raw material contains a kind of gas that is selected from hydrogen, rare gas element and oxidizing gas at least.
31, according to the method for claim 28, wherein the plasma jet raw material contains a kind of boron, nitrogen or the phosphoret(t)ed hydrogen of trace.
32, according to the method for claim 28, wherein collide diamond film epitaxy on described substrate to the diamond substrate by plasma jet.
33, according to the process of claim 1 wherein that described method comprises the steps:
Adopt a plurality of plasma body blowpipes and
Make a plurality of thermal plasmas stream mutually collision in described plasma jet, carbon source being made plasma body, thereby form diamond.
34, according to the method for claim 33, wherein said method may further comprise the steps:
Adopt two direct current plasma blowpipes, the jet of the hydrogen that contains the dissociates hydrogen atomic form is collided mutually in described plasma jet carbon source being made plasma jet, thereby form diamond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109955 CN1029135C (en) | 1987-04-03 | 1991-10-19 | Method and apparatus for vapor deposition of diamond |
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8331887 | 1987-04-03 | ||
| JP083318/87 | 1987-04-03 | ||
| JP220437/87 | 1987-09-04 | ||
| JP245853/87 | 1987-10-01 | ||
| JP250598/87 | 1987-10-06 | ||
| JP257632/87 | 1987-10-13 | ||
| JP257635/87 | 1987-10-13 | ||
| JP320142/87 | 1987-12-19 | ||
| JP330130/87 | 1987-12-28 | ||
| JP63003043A JPH01179789A (en) | 1988-01-12 | 1988-01-12 | Vapor growth method for diamond and thermal plasma deposition method and plasma injection device |
| JP003043/88 | 1988-01-12 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109955 Division CN1029135C (en) | 1987-04-03 | 1991-10-19 | Method and apparatus for vapor deposition of diamond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN88101737A CN88101737A (en) | 1988-10-26 |
| CN1028772C true CN1028772C (en) | 1995-06-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88101737 Expired - Fee Related CN1028772C (en) | 1987-04-03 | 1988-04-02 | Method and apparatus for vapor deposition of diamond |
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| Country | Link |
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| CN (1) | CN1028772C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500951C (en) * | 2007-02-07 | 2009-06-17 | 吉林大学 | Device and method for high-speed growth of diamond single-crystal |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5941647A (en) * | 1996-08-19 | 1999-08-24 | Citizen Watch Co., Ltd. | Guide bush and method of forming hard carbon film over the inner surface of the guide bush |
| EP2425685B1 (en) * | 2009-05-01 | 2016-10-26 | The Regents Of The University Of Michigan Office Of Technology Transfer | In-situ plasma/laser hybrid scheme |
| CN103320829B (en) * | 2013-06-06 | 2016-04-13 | 大连理工大学 | A kind of solution preparation method for electrochemical synthesis diamond thin |
| CN103553036A (en) * | 2013-09-29 | 2014-02-05 | 陈晖� | Circuit for synthesis of diamond |
| CN107267952B (en) * | 2017-05-05 | 2023-05-23 | 宁波工程学院 | Method for plating diamond film by chemical vapor deposition |
| US11518680B2 (en) * | 2017-08-15 | 2022-12-06 | Sumitomo Electric Industries, Ltd. | Body obtained by processing solid carbon-containing material, producing method thereof, and producing apparatus thereof |
| CN108217644B (en) * | 2018-03-05 | 2020-02-14 | 武汉大学 | Method and device for removing hydrogen impurities in preparation process of n-type phosphorus-doped diamond film |
| CN112897477B (en) * | 2021-02-03 | 2022-06-10 | 吉林大学 | Preparation method of polyhedral titanium selenide nanocrystal |
-
1988
- 1988-04-02 CN CN 88101737 patent/CN1028772C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500951C (en) * | 2007-02-07 | 2009-06-17 | 吉林大学 | Device and method for high-speed growth of diamond single-crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN88101737A (en) | 1988-10-26 |
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