CN1102034A - Microwave enhanced CVD system under magnetic field - Google Patents
Microwave enhanced CVD system under magnetic field Download PDFInfo
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- CN1102034A CN1102034A CN94106740A CN94106740A CN1102034A CN 1102034 A CN1102034 A CN 1102034A CN 94106740 A CN94106740 A CN 94106740A CN 94106740 A CN94106740 A CN 94106740A CN 1102034 A CN1102034 A CN 1102034A
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- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims description 224
- 239000000758 substrate Substances 0.000 claims description 95
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- 238000006243 chemical reaction Methods 0.000 claims description 66
- 230000008569 process Effects 0.000 claims description 55
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- H01L21/203—
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
本发明展示一种改进的化学气相淀积法，在这种 方法中，回旋共振与光或等离子体化学气相淀积法相 配合，以高的淀积速度淀积具有高性能的薄膜。高淀 积速度归因于回旋共振，而高质量性能归因于两种化学气相淀积法(CVDs)的组合。
The present invention demonstrates an improved chemical vapor deposition method in which cyclotron resonance cooperates with optical or plasma chemical vapor deposition to deposit high performance thin films at high deposition rates. The high deposition rate is due to cyclotron resonance, while the high quality performance is due to the combination of two chemical vapor deposition methods (CVD s ).
Description
The present invention relates to utilize microwave chemical gas-phase deposition enhanced (CVD) system in magnetic field, more precisely, it relates to electron cyclotron resonace (ECR) chemical vapor deposition (CVD) system.
In film generation technique field, known light reinforcing chemical gas inter-deposition method is arranged, it is than general CVD, and (for example heating power CVD and plasma enhanced CVD) is superior, because it can realize the deposit of film under not damaging the lower temperature of the semiconductor surface of film former thereon.Light strengthens CVD and also has the advantage of a kind of what is called " surface migration ".That is, the atom of illuvium or molecule are preserved their activation energy after being deposited on substrate surface, just because this activation energy, make these atoms or molecular motion and also can not carry out forming film on that part of substrate surface of deposit; Thereby found a kind of method of formation that on rough substrate surface, produces the topped coating of improved substep with CVD.
Yet light strengthens the film formation speed of CVD and considers that from commercial interest required high speed is also poor far.(now having proposed needs deposition speed is improved tens times).
On the other hand, known a kind of utilization makes process gas become the plasma CVD of the glow discharge of plasma by means of high frequency or DC power supply.The advantage of this technology is can deposit under lower temperature.Especially, when the deposition of amorphous silicon thin layer, in and complex centre on the thin layer and drop into hydrogen or fontanel element simultaneously so that easily obtain to have the lead end or the p-n junction of improved characteristics.This plasma CVD also is enough to adapt to the requirement of high rate deposition.
In addition, known a kind of CVD that utilizes electron cyclotron resonace (ECR),, can become to have the thick film of 5000 dust to 10 micron thickness with the speed deposit of 10 dust/seconds to 100 dust/seconds according to this technology.Yet the Surface runoff that reacting gas is parallel to substrate makes that this technology can not be at recess, (for example in groove) film former.Remove this part, make the frequency resonance of ar atmo with 2.47 gigahertzs, the high-intensity magnetic field that this needs 857 Gausses makes air core coil very huge.As a result, owing to can be used for discharging the limited space system of gas, even the standard of the 10% thickness fluctuating of the sacrificial property of possibility on 3 inches disks.
Therefore, the purpose of this invention is to provide and a kind ofly have high deposition speed and do not damage the improved chemical gas-phase precipitation system and the method for the characteristic performance of illuvium.
Fig. 1 is the end view of the part section of the expression first embodiment of the present invention.
Fig. 2 is the end view of the part section of the expression second embodiment of the present invention.
Fig. 3 is the end view of the part section of the expression third embodiment of the present invention.
According to the present invention, mainly come activated reactions gas by cyclotron resonance. Be excited gas dispense in reaction compartment, and in reaction compartment, process gas generation chemical reaction is to carry out the deposit of film. The present invention gets ECR CVD and light strengthens or the advantage of glow discharge CVD; ECR CVD is preponderating aspect the high deposition speed, and glow discharge and light enhancing CVD are preponderating aspect the uniformity of deposition film. For example, when strengthening the CVD deposited amorphous silicon thin film with glow discharge and light, its deposition speed is respectively 1 A/min and 0.1 A/min.
Glow discharge CVD and light are strengthened CVD and electron cyclotron resonace (ECR) the CVD use that combines.This combination makes and might reach very high deposition speed under the situation of not damaging uniformity of film.Under the situation of deposited amorphous silicon thin film, when when light strengthens CVD and matches, its deposition speed be 5 dusts/minute to 20 dusts/minute; When cooperating with glow discharge CVD, its deposition speed be 20 dusts/minute to 100 dusts/minute.
In most preferred embodiment, with in addition in reaction or the inert gas or the nonproductive gas that all can not produce solid matter after decomposing realize cyclotron resonance.Usually use argon gas as inert gas.But, also can use helium, neon or krypton gas.Oxide gas, for example oxygen, nitrogen oxide (N
2O, NO, NO
2), carbonoxide (CO, CO
2), water (H
2O) or nitride gas for example nitrogen, ammonia, hydrazine (N
2H
4), nitrogen fluoride (NF
3, N
2F
6) or their mixtures after control gaseous or diluted in hydrogen, can be used as nonproductive gas.
Silicide gas, for example Si
nH
2n+1(n 〉=1), SiF
n(n 〉=2), SiH
nF
4-n(4 〉=n 〉=1); Germanium compound, for example GeH
4, GeF
4, GeH
nF
4-n(n=1,2,3), aluminium compound, for example Al(CH
3)
3, Al(C
2H
5)
3, AlCl
3Or gallium compound, for example Ga(CH
3)
3And Ga(C
2H
5)
3Above gas is used as process gas and introduces reaction compartment, and they produce the solid matter that is deposited by means of chemical reaction or decomposition.In addition, the impurity gas of interpolation, for example B
2H
6, BF
3, PH
3, or AsH
3Can be blended in the nonproductive gas.
Activate nonproductive gas with cyclotron resonant method, and it is introduced reaction compartment; In reaction compartment, nonproductive gas mixes with process gas, and gives process gas with energy.In this process, process gas is fully activated, and obtains almost the energy of necessity of 100%.This energy of process gas is " potential ", and is diffused in and has glow discharge or ultraviolet entire reaction space.Under this atmosphere, in room temperature or be lower than the deposit of carrying out film under 500 ℃ the temperature.
According to of the present invention, be equipped with under the situation of light enhancing CVD system, even can produce deposit at the inwall of a deep trouth.The experimental result of thin film deposition shows, has 1 micron diameter for one, the open slot of 4 micrometer depth, and when the film thickness on the horizontal surface was 0.5 micron, the film thickness on the groove inwall was 0.3 to 0.45 micron.
In addition, when deposition of semiconductor film on the transparent conductive film with reticulate structure when constituting solar cell, according to the present invention, can generate semiconductive thin film with rough two apparent surfaces.This film shaped shape that helps improving conversion efficiency of solar cell is owing to the characteristic of electron cyclotron resonace.
With reference now to Fig. 1,, as the first embodiment of the present invention, is equipped with the plasma CVD system of cyclotron resonance device with diagram method explanation.
This system comprise one that make with stainless steel, have a cover 1 " reative cell 1 ', reaction compartment 1 is defined to wherein.Reative cell 1 ' upper part, constitute one be used for substrate 10 be fixed on the support 10 of reative cell 1 ' the inside '.Have the halogen lamp heater 7 of several Halogen lamp LEDs 7 ' be installed in cover 1 " on.When open reative cell 1 ' cover 1 " time, an inlet that leads to substrate 10 is arranged.Halogen lamp heater 7 ' see through the window 19 that synthetic quartz is made from the upper end is shone substrate 10.In addition, a pair of mesh grid is set, one heater 7 ' and substrate 10 between, another near reative cell 1 ' the bottom.From the frequency of power supply 6 be the high frequency voltage of 13.56 megahertzes or direct voltage be added to grid 20 and 20 '.Because the glow discharge between grid, reaction compartment begins to store plasma gas.Substrate 10 place by grid 20 and 20 ' between the influence of the caused glow discharge of electric field under.
On the other hand, from doped system 13, provide nonproductive gas to the resonance space that limits by the synthetic quartz cylinder by conduit 18.By means of the air core coil that is arranged on cylinder 29 outsides, magnetic field is added to resonance space 2.Simultaneously, from microwave oscillator 3,, the microwave of 2.45 gigahertzs is injected resonance space through isolator 4.Determining of the magnetic flux density that is provided is relevant with the molecular wt of nonproductive gas.Corresponding to added magnetic field, automatically determine the frequency of microwave.At nonproductive gas is under the situation of argon gas, and magnetic field is adjusted in 875 Gausses.
Exist under the condition in magnetic field by means of the effect of magnetic field and microwave, nonproductive gas is along with being energized with microwave resonance, and produces blockage effect.Seeing that after activating fully nonproductive gas is sent to reaction compartment 1 as (for example) electronics that is energized and the ar atmo of being excited.Above grid 20, several annular nozzles 17 are installed; Process gas is introduced into the nonproductive gas stream from nozzle.
In with the interactional process of nonproductive gas, process gas is excited and is become activity.In addition, aperture plate 20 and 20 ' between apply electric field, this electric field causes glow discharge in reative cell.
According to repeatedly testing as can be known, even reaction compartment is positioned at the place quite far away apart from resonance space, for example this distance is 5cm to 20cm, but nonproductive gas remains activity after entering reaction compartment.Different with this configuration, have in the cyclotron resonant CVD device existing, resonance space and pending substrate are each other at a distance of 1cm to 4cm usually; This CVD device often causes producing rough coating.
In addition, the pressure of reative cell and resonance space is maintained at 1 torr to 10
-4Between the torr, better as if remaining on 0.03 torr to 0.001 torr, so that process gas is dispersed in the entire reaction space.Set up this pressure control with the control valve 14 of gas extraction system 11; Control valve 14 is regulated the speed of exhaust of the vacuum pump 9 that matches with turbomolecular pump as auxiliary pump.
Nonproductive gas also is sent to reaction compartment by homogenizer 20, so that be dispersed in entire reaction space 1 equably.Homogenizer 20 ' also play a part stops the anti-resonance space 2 that flows to of active gases.The nozzle 17 of process gas is positioned at the outlet side of homogenizer 20.In this structure, process gas and argon gas are mixed in the parallel quite broad zone of whole and substrate 10 fully.The equal uniform flow that contains the reacting gas of process gas and nonproductive gas, the deposit that produces film with uniform thickness.
The pressure of selective resonance space and reaction compartment is 1 torr to 10
-4Torr is if 0.03 torr to 0.001 torr is better, so that realize resonance and promote that active gases spreads in container.
Even nonproductive gas after 1 the path, also will keep its activation energy pass by (being generally 20-80 centimetre) from the resonance space to the reaction compartment.Under the situation of electron cyclotron resonace CVD, this path has only 1 to 4 centimetre, and this may be the even reason of uneven film thickness.In any case the interference between homogenizer and the nonproductive gas stream is inevitable; This interference loss the energy of nonproductive gas.Therefore, will inevitably reduce film growth rates.Because this reason, homogenizer 20 can be with separately preparation of electrode.That is, can make homogenizer 20 with the cell quartz plate, and having the thin gate configuration of 5 centimetres of grids of 5 cm x under the cell quartz plate.But, do not require under the inhomogeneity situation of deposit in the demanding speed of growth, homogenizer can be removed.Discharge unwanted or unnecessary gas by gas extraction system 11.At the exhaust side of reative cell, a cushion space is set, also help the even of air-flow.
Experiment 1:
This experiment is for according to the first embodiment of the present invention, deposited amorphous silicon thin film on substrate.
As the argon gas of nonproductive gas,, be sent to resonance space 2 with the flow of 50 ml/min by conduit 18.Adjustment has the microwave oscillator 3 of 200 watts of power supplys, to produce the microwave of 2.45 gigahertzs; It is general as long as the power supply between selecting 30 to 500 watts is all applicable.Magnetic flux density is 875 Gausses.On the other hand, the flow with 20 ml/min feeds reaction compartment 1 with single silane gas; In reaction compartment, total pressure remains on 0.003 torr.
On the glass plate substrate of the transparent membrane that coated conducts electricity, deposit is as the crystal silicon coated semiconductor of non-single crystal semiconductor.Discharge unwanted gas by gas extraction system 11.As a result, with deposition speed film formers on substrate 10 of 45 dust/seconds; The temperature of substrate 10 remains on 250 ℃.This speed is 30 times of the known resulting speed of plasma CVD (1.5 dust/second) of employing separately.The uniformity aspect of climax film thickness, have that area is wide 30 centimetres for long 30 cm x, thickness is on 1 micron the film, only observe 10% thickness and rise and fall.
Then, measured the electrical property of this amorphous silicon membrane.The dark conduction rate is 2 * 10
-10Siemens (centimetre)
-1Under the irradiation with 100 milliwatt/square centimeter (AM1) standard light, the light conductance is 7 * 10
-4Siemens (centimetre)
-1These numerical value are resulting poor unlike using known plasma CVD so far.When this amorphous silicon membrane is when having the solar cell of lead end, to have obtained high conversion efficiency.
Further semiconductive thin film is deposited to 1 micron thickness.On film, observe several diameters and be 0.1 to 0.001 micron pore.Compare with prior art, the number of pore has reduced to 1/10.The gained result according to the present invention sees under details in a play not acted out on stage, but told through dialogues with adjusting to the electron microscope that amplifies 100 times, only finds 1 to 3 pore.
When the mixture of b silane gas or monocrystalline silicon gas and fluorinated silane being imported reaction compartment when replacing independent single silane, further improved deposition speed.
Experiment 2:
This tests the system with first embodiment, proves the deposit of silicon oxide film.
Argon gas and oxygen are transported to resonance space 2 as nonproductive gas by conduit 18; For each gas, flow all is 50 ml/min.Adjustment has the microwave oscillator 3 of 200 watts of power supplys, to produce the microwave of 2.45 gigahertzs; 30 watts to 500 watts the power supply that generally is used to produce microwave share.Magnetic flux density is 875 Gausses.On the other hand, the flow feeding reaction space 1 of single silane gas with 20 ml/min; Pressure in the reaction compartment remains on 0.003 torr.
Deposit silicon dioxide or boron glass or phosphorus glass on silicon substrate, the latter is the silicon dioxide of phosphorus or boron of having mixed.Discharge unwanted gas by gas extraction system 11.As a result, with the deposition speed of 45 dust/seconds, on the substrate 10 that keeps 250 ℃ of temperature, generate thin film.This speed is only to use 30 times of the resultant speed of known plasma CVD (1.5 dust/second).Even adopt electron cyclotron CVD separately, can not reach high like this speed.
Before the present invention, people have observed a large amount of silicon atom groups, and it is the silicon atom group who fails to form crystal, have 0.01 to 0.001 micron width.But, according to the present invention, promptly use transmission electron microscope, do not observe atomic group fully yet.Under the situation of 1000 angstroms thick layers insulation, its anti-electric field strength is 6 * 10
6Volt/centimetre, these ordinary skills exceed 30%.
When the mixture with b silane gas or single silane gas and fluorinated silane replaces independent single silane to import reaction compartment, further increased deposition speed.
This experiment is to do for generating silicon nitride film; In this experiment, except argon gas, also with ammonia as nonproductive gas input resonance space, and other steps of this experiment identical with experiment 1 basically.Import than silane gas by conduit 16 or 18 and to Duo 4 times ammonia.
Importing under the situation of ammonia by conduit 18, ammonia can replace argon gas as resonator gas.Use another kind of method, ammonia mixes simply with independent argon gas as resonator gas.But argon gas is more suitable in making resonator gas in resonance space 12 than ammonia, is resonator gas although have only argon gas, and amino molecule also can become enough active with the ar atmo collision of being excited.
Activated fully so contain the mixture of b silane gas and ammonia, and be imported into reaction compartment 1.The mixture of silicon fluoride, nitrogen and hydrogen can be used to replace described mixture.In addition, import in the reaction compartment as process gas with single silane, silicon fluoride or b silane gas respectively and carry out deposit.Pressure in the quantity of every kind of gas and the reaction compartment 1 is identical with experiment 1.As a result, to three kinds of process gas, respectively with 12 dust/seconds, the deposition speed of 18 dust/seconds and 18 dust/seconds obtains silicon nitride film.This deposition speed approximately is ten times with the known resulting deposition speed of plasma CVD; In known plasma CVD system, common speed deposition silicon nitride film with 1.5 dust/seconds.
These are deposited on has 4 * 10
15Atom/(centimetre)
3Silicon nitride films on the n type substrate of impurity concentration, 30 centimetres wide and 30 centimeter length have 8 * 10 respectively
11(centimetre)
-2, 9 * 10
11(centimetre)
-2With 8 * 10
11(centimetre)
-2Horizontal surface density; These values are than the value (1.5 * 10 of common prior art
11(centimetre)
-2) little by 1/3, and roughly with the independent value (8 * 10 that obtains with the ECR deposition process
11(centimetre)
-2) identical.Also obtain improved uniformity of film, wherein the fluctuating of thickness is less than 10%, and the difference of physical characteristic is suitable on the film.
For further reducing horizontal surface density, two step sedimentations may be fit to.That is, at first use up the silicon nitride film that strengthens CVD deposition thickness 50 dust to 200 dusts, then, then, be superimposed upon on the preceding thin film with another layer of electron cyclotron resonace (ECR) CVD deposit silicon nitride film of resonance space with input microwave.
Experiment 4:
Another deposition process of this description of test silicon oxide film.Except hereinafter particularly pointing out, this method method with former experiment basically is identical.Nonproductive gas is the nitrous oxide (dinitrogen monooxide) with nitrogen dilution, rather than ammonia.Pressure in the reaction compartment 1 is 1 * 10
-3Holder is avoided excessive oxidation by this condition.Process gas is monosilane (SiH
4) gas or chlorosilane (SiH
2Cl
2).Deposition speed was 40 dust/seconds.The same with former experiment, also observe the film of deposit at recess.
Experiment 5:
This experiment is used for deposit titanium nitride film.In this experiment, its method is similar to the method for experiment 3, therefore, will only narrate and improve and differential section, and not repeat remainder.
Titanium tetrachloride gases replaces silane gas to be imported into reative cell.Pressure in the reative cell is 1 * 10
-3Torr.With the speed deposits of 40 dust/seconds titanium nitride film as product; 3 the same with experiment, at recess also deposit film.When being used as the passivation film of the mechanical strength that strengthens metal tools, titanium nitride is favourable.
Experiment 6:
This experiment is used for the deposit aluminium nitride film.The method of this experiment is similar to the method for experiment 3, therefore, will only narrate and improve and differential section, and remainder no longer repeats.
By conduit 16 and nozzle 17 with aluminium methyl (Al(CH
3)
3) import as process gas.By the argon gas of conduit 18 transmission as nonproductive gas.As a result, after having carried out deposit in 30 minutes, obtain the aluminium nitride film of 4000 dust thickness.
When being used as passivation film, aluminium nitride is owing to its high heat conductivity is on a good wicket.The general characteristic of the aluminium nitride of Sheng Chenging (AlN) and silicon nitride film is similar like this.
With reference to figure 2, it represents the second embodiment of the present invention.Among the figure, the reative cell made from stainless steel 1 ' have a LOADED CAVITY and a non-LOADED CAVITY at its front and back, these two chambeies are all expressions in the drawings.Reative cell 1 ' in and the adjacent part of load cavity and unsupported chamber, constitute a reaction compartment, owing to seal into airtight construction, so process gas can not leak from reaction compartment with stainless steel wall or isolated material.Or rather, reaction compartment be limited at make the uniform a pair of homogenizer 20 of process gas and 20 ' between.Many substrates 10 be fixed on support 10 ' facing surfaces; Support 10 ' vertically be arranged in the reaction compartment 1.
In the present embodiment, ten of substrate 10 samples be attached to 5 supports 10 ' on.Reative cell 1 ' both sides heater is installed, each heater is made of several Halogen lamp LEDs; Launch ultraviolet ray from these Halogen lamp LEDs, pass synthetic quartz window 19, irradiation substrate 10 and reative cell 1 ' inside.In addition, homogenizer 20 and 20 ' play a part pair of electrodes; High frequency voltage or direct voltage from 13.56 megahertzes of power supply 6 are added to this on the electrode, and in reaction compartment this to setting up electric field between the electrode.Just as shown in FIG., substrate 10 is arranged in parallel with added electric field and embarks on journey.As another selectable scheme, also can on the direction of vertical view, relatively settle these two electrodes.
From doped system 13 with nonproductive gas delivery to make of synthetic quartz, resonance space is limited to wherein cylinder 29.By means of being arranged on cylinder 29 air core coil on every side, magnetic field is added to resonance space 2.Simultaneously, from the microwave of 2.45 gigahertzs of microwave oscillator 3, inject in the resonance space 2 by isolator 4.With the same mode of first embodiment, argon gas is activated, and is introduced into reaction compartment 1 by homogenizer 20.
This method is substantially the same with first embodiment's, therefore saves the explanation about deposition process.
Experiment 7:
This experimental basis second embodiment of the present invention, deposited amorphous silicon thin film on substrate.
Reative cell 1 ' have is high 25 centimetres, wide 40 centimetres, long 40 centimetres reaction compartment.Each batch comprises 10 substrates, and every substrate is wide 20 centimetres, long 30 centimetres.The pressure of reaction compartment is 0.003 torr.Argon gas is with the flow of 200 ml/min, and monosilane is sent to resonance space 2 with the flow of 80 ml/min as nonproductive gas.Microwave oscillator is launched the microwave of 2.45 gigahertzs, 200 watts to 800 watts (for example 400 watts).40 watts of high-frequency electric powers of power supply output.Magnetic flux density is adjusted in 875 ± 100 Gausses.
Scribbling on the glass plate substrate of nesa coating, deposit is as the amorphous silicon semiconductor film of non-single crystal semiconductor.Discharge unwanted gas by gas extraction system 11.Generate film as product with the deposition speeds of 45 dust/seconds on substrate 10, the temperature of substrate 10 remains on 250 ℃.This speed is to use 30 times of the resulting speed of plasma CVD (1.5 dust/second) separately.
Then, measure the electrical characteristics of amorphous silicon membrane.The dark conduction rate is 4 * 10
-10Siemens (centimetre)
-1100 milliwatts/(centimetre)
-2(AMl) under the irradiation, the light conductance is 6 * 10
-5Siemens (centimetre)
-1These data are unlike the data difference that obtains with known plasma CVD so far.When using, observe high conversion efficiency when amorphous silicon membrane and the solar cell with lead end are integrated.
The following describes amorphous silicon is how to be used to solar cell.At first, on substrate, generate the P type semiconductor film with known electric glow discharge method.Then, with electron cyclotron resonace CVD of the present invention one deck pure semiconductor that on P type film, superposes.At last, according to deposit one deck n N-type semiconductor N of the present invention.
Use another kind of method, can make solar cell with multi-chamber system.In this case, one or more reative cells of Ecr plasma CVD have been made.After the support of settling many substrates was put into the loading chamber, substrate and bracing frame were transported first reative cell together; In first reative cell, carry out the P type semiconductor (Si of thickness 100 to 200 dusts
xC
1-x) deposit of film.Then, transported as shown in Figure 2 second reative cell with the support of substrate; In second reative cell, with electron cyclotron CVD method deposit one deck pure semiconductor film of the present invention.Then, support is transported the 3rd reative cell; In the 3rd reative cell, according to deposit one deck n type crystalline state semiconductive thin film of the present invention.That is, the present invention is used to the semiconductor of pure semiconductor of deposit and crystallization.
On the film that generates with the glow discharge sedimentation, have been found that the pore of 0.1 to 0.01 micron of several diameter.With prior art relatively, the number of pore is reduced to about 1/10.According to the present invention, in showing, details in a play not acted out on stage, but told through dialogues only finds 1 to 3 pore with the electron microscope that is adjusted in 100 times of amplification quantity.
When the mixture with b silane gas or monosilane gas and fluorinated silane replaces independent monosilane importing institute to answer the space, further improved deposition speed.
Experiment 8:
This experiment is used to generate silicon nitride film; In this experiment, except testing the configuration of 7 process, also provide ammonia as nonproductive gas.By conduit 16 or 18, import ammonia with 5 times of flows to silane.
Importing under the situation of ammonia by conduit 18, ammonia can replace argon gas as resonator gas.Use another kind of method, ammonia mixes simply with independent argon gas as resonator gas.But, argon gas is more suitable in as resonator gas than ammonia.Although argon gas is a resonator gas and ammonia is not, in resonance space 2, the ar atmo collision that amino molecule also can coactivation is also activated fully.
Therefore, the mist of being made up of b silane gas and ammonia is activated and is imported into reaction compartment 1 fully.Can use the mixture of silicon fluoride, nitrogen and hydrogen to replace above-mentioned mist.Then,, import reaction compartment and carry out deposit as process gas with silyl fluoride, silicon fluoride or disilane.The flow of every kind of gas and the pressure in the reaction compartment are identical with experiment 1.As a result, for three kinds of process gas, respectively with 12 dust/seconds, the deposition speed of 18 dust/seconds and 18 dust/seconds obtains silicon nitride film.These deposition speeds approximate ten times with the known resultant speed of plasma CVD method; In known plasma CVD, common speed deposition silicon nitride film with 1.5 dust/seconds.
Two step sedimentations are applicable to further reducing horizontal surface density.Promptly at first use up and strengthen the silicon nitride film that the CVD deposit has 50 to 200 dust thickness; Then, then, be superimposed upon on the film of deposit in the past with another layer of electron cyclotron resonace (ECR) CVD deposit silicon nitride film with microwave enhancing resonance space.
Experiment 9:
The another kind of silica membrane deposition process of this description of test.Except hereinafter particularly pointing out, this process experimentation with former basically is identical.Nonproductive gas is with nitrous oxide gas behind the nitrogen dilution rather than ammonia.Pressure in the reaction compartment 1 is 1 * 10
-3Torr stops over oxidation whereby.Process gas is monosilane (SiH
4) gas or chlorinated silane (SiH
2Cl
2).Deposition speed was 40 dust/seconds.Identical with in the former experiment also observes the film of institute's deposit at recess.
Experiment 10:
This experiment relates to the deposit of titanium nitride.Therefore its process, only will disclose and test 8 different steps, and not repeat remainder to carry out with the 8 identical modes of experiment.
In this experiment, the titanium chloride of using nitrogen dilution is imported into reaction compartment 1 by conduit 16 from nozzle 17.The mist of nitrogen and hydrogen also is imported into resonance space 2 with argon gas together.As a result, by 10 minutes deposition process, deposit have a titanium nitride membrane of 4000 dust thickness.
Titanium nitride membrane is favourable aspect wear resistence.The gloss of the film that obtains according to the present invention is equivalent to the result that obtains with first system technology.
Referring now to Fig. 3, illustrate that the cyclotron resonance type light as the 3rd embodiment strengthens the CVD system.
In the drawings, the reative cell of making by stainless steel 1 ' in constitute reaction compartment 1.Reative cell 1 ' the top install by if the heater 7 that gets up in individual Halogen lamp LED 7 equipments '.By support 10 ' constitute two relative sidewalls of reative cell; With support 10 ' with substrate 10 be supported on heater 7 ' under.Infrared ray by Halogen lamp LED 7 ' emission passes the window made from synthetic quartz 19, heated substrate 10.In the bottom of reative cell 1, with several Cooper-Hewitt lamps 6 equipment light source chambers 6 '.By light source 6 ' in the ultraviolet ray of mercury vapor lamp 6 emission pass the light window made by the synthetic quartz bottom surface of irradiation substrate 10 again; The light window has high transmission coefficient in short wavelength range.Cooper-Hewitt lamp be used for greater than 5 milliwatts/(centimetre)
2Irradiance (preferably with 185 millimicrons of wavelength 10-100 milliwatts/(centimetre)
2Irradiance) irradiation substrate 10.
On the other hand, nonproductive gas is imported the resonant cavity made from synthetic quartz 2 from doped system by conduit 18.Resonant cavity 2 be equipped with air core coil 5 and 5 '; In resonant cavity, produce magnetic field by air core coil.In addition, by isolator 4 microwave of 2.45 gigahertzs is transported to resonant cavity from oscillator 3.All the time determine magnetic field intensity and microwave frequency according to the molecular weight of nonproductive gas.If use argon gas as nonproductive gas, magnetic field intensity can be 875 Gausses.Microwave frequency during with hydrogen is automatically calculated.
By means of magnetic field, nonproductive gas and microwave resonance, and therefore increase energy, be pinched in the resonant cavity.Then, the nonproductive gas that is activated is by as the dividing plate 20 of homogenizer ' be admitted to reaction compartment 1.Process gas also passes through annular nozzle 17 from doped system, the reaction compartment 1 of being released.As a result, activate process gas with the nonproductive gas that is activated.In addition, also give process gas energy by ultraviolet irradiation.
According to experimental result, quite far away even reaction compartment leaves resonance space, for example distance is 5 to 20 centimetres, and it is active that nonproductive gas remains in reaction compartment.Different with this structure, according to widely used existing CVD device with cyclotron resonance, general resonance space and apart 1 to 4 centimetre of pending substrate, this often causes producing rough coating.
In addition, the pressure with reative cell and resonance space is controlled at 1 to 10
-4Torr preferably is controlled at 0.03 to 0.001 torr, so that process gas can easily be dispersed in the entire reaction space.The control valve 14 of gas extraction system 11 is regulated and deflation rate as the vacuum pump 9 of turbomolecular pump (the not expressing in the drawings) coupling of auxiliary pump, to realize pressure control.
Nonproductive gas is also by homogenizer 20 ' be sent to reaction compartment 1, so that make it be dispersed in entire reaction space 1.For the used nozzle 17 of process gas is positioned at the downstream of the process gas of being supplied with, as seeing from homogenizer.In this structure, on the whole broad plane that is parallel to substrate, process gas and argon gas mix each other fully.Comprise that the equal uniform flow of the reacting gas of process gas and nonproductive gas has the deposit of the film of uniform thickness subsequently.
Much less, the interference between homogenizer 20 ' nonproductive gas stream is inevitably, thus loss the energy of nonproductive gas.Therefore, formation speed certainly will will reduce.For this reason, at the high formation speed of needs rather than require the inhomogeneity occasion of deposit, can remove homogenizer.Discharge unwanted or unnecessary gas by gas extraction system 11.
Experiment 11:
This experiment is according to third embodiment of the present invention deposited amorphous silicon thin film.
In this experiment, with argon gas as nonproductive gas, with the flow volume delivery of 50 ml/min to reaction compartment; And monosilane is imported reaction compartment simultaneously with the flow of 20 ml/min, mix with argon gas.Pressure in the reative cell is maintained at 0.002 torr.Produce the ultraviolet irradiation of 185 millimicrons of wavelength with Cooper-Hewitt lamp.Shaking with 30 to 500 watts power adjustment microwaves, to make its frequency be 2.45 gigahertzs to device, and the most handy 30 to 200 watts power supply is regulated.With the corresponding magnetic flux density of the microwave of this frequency, be chosen as 875 Gausses.
Amorphous silicon membrane is deposited on the glass of coated transparent conductive film on substrate.During the amorphous silicon of deposit, discharge unwanted gas by gas extraction system as non-monocrystalline silicon.As a result, under 250 ℃ of temperature, deposition speed was 13 dust/seconds.This speed is to use up 40 times that strengthen the resulting speed of CVD.The surface of transparent membrane has reticulate structure, is rough surface.And on this rough surface, carried out deposit equally.
The dark-conductivity of the amorphous silicon membrane of Sheng Chenging is 3 * 10 like this
-10Siemens (centimetre)
-1With respect to the AMl(100 milliwatt/(centimetre)
2) standard light, the photoconductivity of amorphous silicon membrane is 6 * 10
-5Siemens (centimetre)
-1These numerical value are equivalent to the numerical value that existing amorphous solar cell reaches basically.Use solar cell, have and be not less than the conversion efficiency that obtains with prior art according to noncrystal membrane of the present invention equipment.
In addition, on the semiconductive thin film that is deposited to 1 micron thickness, observe the pore of 0.1 to 0.001 micron of several diameter.Compare the decreased number to 1/10 of pore with prior art.See under details in a play not acted out on stage, but told through dialogues with the electron microscope that amplifies 100 times and only to find 1 to 3 pore.
When the mist with b silane gas or monosilane gas and fluorinated silane replaces independent monosilane gas to import reaction compartment, further improved deposition speed.
Experiment 12:
This experiment is used to generate silicon nitride film; In this experiment, except argon gas, ammonia also is used as nonproductive gas and sends in the resonance space; Other processes of this experiment basically with the experiment 11 identical.By conduit 16 or 18, the ammonia amount of importing is 5 times of silane import volume.
When importing ammonia by conduit 18, ammonia can replace argon gas as resonator gas.Another kind method is mixed ammonia simply with independent argon gas as resonator gas.But argon gas is more suitable in as resonator gas than ammonia.Although having only argon gas is resonator gas, and amino molecule collides with the hydrogen atom of being excited in resonance space 2, thereby is also activated fully.
Therefore, the mist that comprises b silane gas and ammonia is activated fully and is imported in the reaction compartment 1.The mist of silicon fluoride, nitrogen and hydrogen can be used to replace above-mentioned mist.In addition, use monosilane respectively, silicon fluoride or disilane import reaction compartment as process gas and carry out deposit.Identical in pressure in every kind of gas flow and the reaction compartment 1 and the experiment 1.As a result, for three kinds of process gas, respectively with 12 dust/seconds, the deposition speed of 18 dust/seconds and 18 dust/seconds obtains silicon nitride film.These deposition speeds approximately are ten times with the known resulting speed of plasma CVD; In known plasma CVD, common speed deposit silicon nitride with 1.5 dust/seconds.
Have 4 * 10
15Atom/centimetre
3The n type substrate of impurity concentration on these 30 centimetres wide and the silicon nitride film of 30 centimeter length, have 8 * 10 respectively
11(centimetre)
-2, 9 * 10
11(centimetre)
-2With 8 * 10
11(centimetre)
-2Horizontal surface density, this is less than common prior art value (1.5 * 10
12) 1/3, and roughly with independent use electron cyclotron resonace sedimentation income value (8 * 10
12) identical.And uniformity of film also is improved, and its thickness rises and falls less than 10%, and the difference of physical characteristic is suitable on the film.
Can adopt two step sedimentations for further reducing horizontal surface density.That is, at first use up the silicon nitride film that enhancing CVD deposit has 50 to 200 dust thickness, then, then strengthen another layer of ECR CVD deposit silicon nitride film, be superimposed upon on the film of deposit in the past with microwave with resonance space.
Experiment 13:
This experiment is used to generate silicon nitride film; In this experiment, except testing 10 configuration, also ammonia is supplied as nonproductive gas, it is by conduit 16 or 18, with 5 times of flows importing ammonias to silane.
When importing ammonia by conduit 18, ammonia can replace argon gas as resonator gas.Another kind method is mixed ammonia simply with independent argon gas as resonator gas.But argon gas is more suitable in as resonator gas than ammonia.Although having only argon gas is resonator gas, and amino molecule also collides with the ar atmo of being excited in resonance space 2, and is activated fully.
Therefore, the mist that comprises disilane and ammonia is activated fully and is imported in the reaction compartment 1.The mist of also available silicon fluoride, nitrogen and hydrogen replaces above-mentioned mist.In addition, monosilane, silicon fluoride or b silane gas are imported reaction compartment as process gas.Pressure in the content of every kind of gas and the reaction compartment 1 is identical with experiment 10.As a result, for three kinds of process gas, respectively with 12 dust/seconds, the deposition speed of 18 dust/seconds and 18 dust/seconds obtains silicon nitride film.These deposition speeds are to use up to strengthen more than 20 times of CVD gained speed; Strengthen among the CVD common speed deposition silicon nitride film with 0.3 dust/second at light.
Have 4 * 10
15Atom/centimetre
3These silicon nitride films on the n type substrate of impurity concentration have 2 * 10 respectively
11(centimetre)
-2, 2.5 * 10
11(centimetre)
-2With 2.5 * 10
11(centimetre)
-2Horizontal surface density, though this is greater than strengthening the resulting numerical value of CVD with the light that has earlier, less than with common prior art plasma CVD income value 1/7 and have 1/4 of cyclotron resonant CVD income value less than usefulness.
Can adopt two step sedimentations for further reducing horizontal surface density.That is, at first use up the silicon nitride film that enhancing CVD deposit has 50 to 200 dust thickness, then, then strengthen another layer of ECR CVD method deposit silicon nitride film, be superimposed upon on the film of deposit in the past with microwave with resonance space.
Equally has the deposit that has realized silicon nitride film on 1.5 microns wide and the 4 micrometers deep trench substrates.Give the fixed film that generates 0.3 micron thickness by deposit.In groove, obtain having the silicon nitride film of 0.3 micron thickness.
Experiment 14:
The another kind of deposition process of this description of test silicon oxide film.Except hereinafter particularly pointing out, this method method with last experiment basically is identical.Oxidation b silane gas with nitrogen dilution replaces ammonia as nonproductive gas.Pressure in the reaction compartment 1 is 1 * 10
-3Torr prevents over oxidation whereby.Process gas is monosilane (SiH
4) gas or chlorinated silane gas (SiH
2Cl
2).Deposition speed was 20 dust/seconds.The same with in the last experiment also observed the film of deposit at recess.
Experiment 15:
This experiment is used for the deposit aluminium nitride film.The method of this experiment is similar with experiment 14, therefore will only narrate improved and different piece, and remainder does not repeat.
Import trimethyl aluminium (Al(CH by conduit 16 and nozzle 17
3)
3) as process gas.By the argon gas of conduit 18 conveyings as nonproductive gas.As a result, after deposit in 10 minutes, obtain the aluminium film of 700 dust thickness.
In the present embodiment, even generate aluminium nitride film at window 20, it also will not hinder the ultraviolet optical transmission, because the energy gap of aluminium nitride is 6 electron-volts.This makes might make separately to use up and strengthens a kind of light reflection protecting film with adequate thickness of CVD generation.
Aluminium nitride is because its high heat conductivity, thereby is favourable when quilt is used as passivating film.The general performance of the aluminium nitride of Sheng Chenging (Al N) is similar to silicon nitride film like this.
When we illustrate particularly and narrate most preferred embodiment of the present invention, the professional in present technique field will understand, under the situation of the spirit and scope of the present invention, can be exemplified below making various changes on its form and the details:
Before actual deposition film, can import nitrogen fluoride (NF by the nozzle shown in Fig. 3 17
2) gas, hydrogen (H
2) or nitrogen (N
2), clean with the optics that carries out substrate surface, making to produce becomes repeatably.This optics cleans and can also can carry out with the fluorine atom or the chlorine atom of activity with active hydrogen atom.Optics by means of fluorine or chlorine cleans, can be from surface removal oxide or other dust.In addition, optics cleans the oxide-free film that forms the antioxygen G﹠W from the teeth outwards.This optics cleans the high-quality that has guaranteed deposition film, because tend to damage deposition process from the oil vapour pollution of gas extraction system.
Excimer laser (100 to 400 millimicrons of wavelength), argon laser, nitrogen laser or the like can be used as light source of the present invention.
Substrate can be a glass plate, corrosion resistant plate or deposit III thereon-V family semiconducting compound such as GaAs (Ga As), aluminum gallium arsenide (Ga Al As), the silicon semiconductor substrate of indium phosphide (In P) or gallium nitride (Ga N) or the like.
Strengthen CVD and carry out Al when using up, PSG, BSG, Ga N during the deposit of Ga P or Al P, can use Al(CH respectively
3)
3, Si
2H
6And O
2And PH
3(or P
2H
6) synthetic Ga(CH
3)
3And NH
3Synthetic, Ga(CH
3)
3And PH
3Synthetic or Al(CH
3)
3And PH
3Synthetic as process gas.
Amorphous semiconductor Si Ge
1-x(0＜X＜1), SiO
2-x(0＜X＜2), SiC
1-x(0＜X＜1), Si
3N
4-x(0＜X＜4) can replace amorphous silicon semiconductor.
When applying the present invention to metal insulator silicon (MIS) type light emitting devices, field-effect transistor (FETs), superlattice device (super lattice devices), the HEMT device, semiconductor laser during optic integrated circuit or the like, also is extremely favourable.
Though more than narrated the desirable cyclotron resonance deposition system that utilizes magnetic field with suitable adjustment and corresponding tuning microwave,, can only utilize microwave fully to encourage nonproductive gas, thereby obtain fast deposition speed.
Claims (49)
1, a kind of apparatus for processing plasma is characterized in that, it comprises:
One reative cell;
One gas imported unit will be handled gas and introduce this reative cell;
One microwave launcher is injected microwave in this reative cell with a predetermined direction by the wall of this reative cell;
One magnetic field inducing device, inducing magnetic field in reative cell and form electron cyclotron resonace is so that said processing gas changes plasma into;
One substrate has a pending surface, and is placed in the reative cell, so that said substrate leaves the wall of said reative cell; And
Wherein the space between reative cell and said substrate is unrestricted, also is unrestricted so that said plasma arrives flowing of said substrate from said reative cell.
2, according to the equipment of claim 1, it is characterized in that, in reative cell, also comprise the device of an inducing field.
3, according to the equipment of claim 2, it is characterized in that, substrate is placed in the reative cell, make a surface of substrate be substantially perpendicular to said electric field.
4, according to the equipment of claim 2, it is characterized in that, substrate is placed in the reative cell, make that a surface of substrate is parallel with said electric field basically.
According to the equipment of claim 2, it is characterized in that 5, said electric field is a direct current (DC) electric field.
According to the equipment of claim 2, it is characterized in that 6, said electric field is a high-frequency radio frequency (RF) electric field.
According to the equipment of claim 1, it is characterized in that 7, the frequency of said microwave is 2.45 gigahertzs (GHz), and said magnetic field is 875 Gausses.
8, a kind of apparatus for processing plasma is characterized in that it comprises:
One reative cell;
One gas imported unit will be handled gas and introduce this reative cell;
One microwave launcher is injected microwave in this reative cell with a predetermined direction;
One magnetic field inducing device, inducing magnetic field in reative cell and form electron cyclotron resonace is so that said processing gas changes plasma into; And
One substrate has a pending surface, and is placed in the reative cell, so that said substrate leaves said magnetic field inducing device with said predetermined direction;
Wherein the space between said magnetic field inducing device and said substrate is unrestricted, so that flowing of the space of said plasma from said magnetic field inducing device to said substrate also is unrestricted.
9, equipment according to Claim 8 is characterized in that, also comprises the device of an inducing field in reative cell.
10, according to the equipment of claim 9, it is characterized in that, substrate is placed in the reative cell, make a surface of substrate be substantially perpendicular to said electric field.
11, according to the equipment of claim 9, it is characterized in that, substrate is placed in the reative cell, make that a surface of substrate is parallel with said electric field basically.
According to the equipment of claim 9, it is characterized in that 12, said electric field is a direct current (DC) electric field.
According to the equipment of claim 9, it is characterized in that 13, said electric field is a high-frequency radio frequency (RF) electric field.
14, dirty according to Claim 8 equipment is characterized in that, the frequency of said microwave is 2.45 gigahertzs (GHz), and the intensity in said magnetic field is 875 Gausses.
15, a kind of apparatus for processing plasma is characterized in that, it comprises:
One plasma forms the chamber;
One gas imported unit will be handled gas and introduce this plasma formation chamber;
One microwave launcher is injected this plasma with a predetermined direction with microwave and is formed in the chamber;
One magnetic field inducing device forms inducing magnetic field in the chamber and forms electron cyclotron resonace at plasma, so that said processing gas changes plasma into; And
One object process chamber adjoins plasma and forms the chamber, and the size of the opening between plasma formation chamber and the object process chamber cross-sectional area with plasma formation chamber at least is the same big;
One substrate has a pending surface, and is placed in the object process chamber;
Because the size of said opening, it is unrestricted that said plasma forms chamber to the mobile of said substrate from said plasma.
16, according to the equipment of claim 15, it is characterized in that, in the object process chamber, also comprise the device of an inducing field.
17, according to the equipment of claim 16, it is characterized in that, substrate is placed in the object process chamber, make a surface of substrate be substantially perpendicular to said electric field.
18, according to the equipment of claim 16, it is characterized in that, substrate is placed in the object process chamber, make that a surface of substrate is parallel with said electric field basically.
According to the equipment of claim 16, it is characterized in that 19, said electric field is a direct current (DC) electric field.
According to the equipment of claim 16, it is characterized in that 20, said electric field is a high-frequency radio frequency (RF) electric field.
According to the equipment of claim 15, it is characterized in that 21, the frequency of said microwave is 2.45 gigahertzs (GHz), and the intensity in said magnetic field is 875 Gausses.
22, a kind of method of plasma processing is characterized in that it comprises:
Handle gas with one and introduce a reative cell;
Wall by reative cell injects this reative cell with a predetermined direction with microwave;
With magnetic field inducing device inducing electromagnetic field and form electron cyclotron resonace in reative cell, so that change said processing gas into plasma; And
One substrate with pending surface is seated in the reative cell; So that said substrate leaves the wall of said reative cell;
Wherein, the space between the wall of reative cell and the said substrate is unrestricted, thereby said plasma also is unrestricted by said reaction chamber apparatus to flowing of said substrate.
According to the method for claim 22, it is characterized in that 23, it is included in inducing one electric field in the reative cell.
24, according to the method for claim 23, it is characterized in that, substrate is placed in the reative cell, make a surface of substrate be substantially perpendicular to said electric field.
25, according to the method for claim 23, it is characterized in that, substrate is placed in the reative cell, make that a surface of substrate is parallel with said electric field basically.
According to the method for claim 23, it is characterized in that 26, said electric field is a direct current (DC) electric field.
According to the method for claim 23, it is characterized in that 27, said electric field is a high-frequency radio frequency (RF) electric field.
According to the method for claim 27, it is characterized in that 28, the frequency of said microwave is 2.45 gigahertzs (GHz), and the intensity in said magnetic field is 875 Gausses.
29, according to the method for claim 22, it is characterized in that, deposit skim at said substrate surface from said processing gas.
According to the method for claim 22, it is characterized in that 30, said substrate surface is by said processing gas etching in addition.
31, a kind of method of plasma processing is characterized in that, it comprises:
To handle gas and introduce reative cell;
With a predetermined direction microwave is injected in this reative cell;
In reative cell, form electron cyclotron resonace, so that said processing gas changes plasma into inducing device inducing magnetic field, a magnetic field; And
To have a pending surface and be placed in the reative cell, so that said substrate leaves said magnetic field inducing device with said predetermined direction;
Wherein the space between said magnetic field inducing device and said substrate is unrestricted, so that space mobile of said plasma from said magnetic field inducing device to said substrate is unrestricted.
32, according to the method for claim 31, it is characterized in that, in reative cell, also comprise the device of an inducing field.
33, according to the method for claim 32, it is characterized in that, substrate is placed in the reative cell, make a surface of substrate be substantially perpendicular to said electric field.
34, according to the method for claim 32, it is characterized in that, substrate is placed in the reative cell, make that a surface of substrate is parallel with said electric field basically.
According to the method for claim 32, it is characterized in that 35, said electric field is a direct current (DC) electric field.
According to the method for claim 32, it is characterized in that 36, said electric field is a high-frequency radio frequency (RF) electric field.
According to the method for claim 31, it is characterized in that 37, the frequency of said microwave is 2.45 gigahertzs (GHz), and the intensity in said magnetic field is 875 Gausses.
38, according to the method for claim 31, it is characterized in that, on said substrate, deposit skim by said processing gas.
39, according to the method for claim 31, it is characterized in that, with the said substrate surface of said processing gas etching.
40, a kind of method of plasma processing is characterized in that it comprises:
Handle gas with one and introduce plasma formation chamber;
With a predetermined direction microwave is injected this plasma and form the chamber;
Form inducing electromagnetic field in the chamber and form electron cyclotron resonace at this plasma, so that change said processing gas into plasma;
Adjoin plasma formation device place and establish an object process chamber, the size of an opening between plasma formation chamber and the object process chamber cross-sectional area with plasma formation chamber at least is the same big;
One substrate with pending surface is seated in the object process chamber; And
Because the size of said opening, it is unrestricted to the mobile of said substrate that said plasma forms the chamber by said gas ions.
According to the method for claim 40, it is characterized in that 41, it also is included in inducing one electric field in the object process chamber.
42, according to the method for claim 41, it is characterized in that, substrate is placed in the reative cell, make a surface of substrate be substantially perpendicular to said electric field.
43, according to the method for claim 41, it is characterized in that, substrate is placed in the object process chamber, make that a surface of substrate is parallel with said electric field basically.
According to the method for claim 41, it is characterized in that 44, said electric field is a direct current (DC) electric field.
According to the method for claim 41, it is characterized in that 45, said electric field is a high-frequency radio frequency (RF) electric field.
According to the method for claim 40, it is characterized in that 46, the frequency of said microwave is 2.45 gigahertzs (GHz), and the intensity in said magnetic field is 875 Gausses.
47, according to the method for claim 40, it is characterized in that, on said substrate surface, deposit skim by said processing gas.
48, according to the method for claim 40, it is characterized in that, with the said substrate of said processing gas etching.
49, a kind of process for chemical vapor deposition of materials with via is characterized in that, it comprises:
Handle gas with one first and introduce in the reative cell, this first gas is to select from the combination of argon, nitrogen, ammonia, hydrazine, nitrogen fluoride, hydrogen and their mixture;
In said reative cell, form magnetic field in said reative cell, to set up an electron cyclotron resonace, so that change said first gas into plasma by the input microwave with in said chamber;
Handle gas with one second and import said reative cell, second to handle gas be to close gas and a calorize is closed a kind of gas of selecting the combination of gas from a titanizing for this;
Control said first and handle gas, so that its part energy is given and the said second processing gas;
Be seated in bias electrode in the said reative cell by at least one, energy be input to said first and second handle gases; And
On a substrate surface of inserting in said reative cell, form the thin layer in the combination that one deck is selected from titanium nitride and aluminium nitride.
Applications Claiming Priority (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP228077/1985 | 1985-10-14 | ||
| JP22808285A JPS6289875A (en) | 1985-10-14 | 1985-10-14 | Thin film forming device |
| JP60228080A JPS6289874A (en) | 1985-10-14 | 1985-10-14 | Formation of thin film |
| JP228080/85 | 1985-10-14 | ||
| JP22807785A JPS6286165A (en) | 1985-10-14 | 1985-10-14 | Formation of thin film |
| JP228083/85 | 1985-10-14 | ||
| JP228082/1985 | 1985-10-14 | ||
| JP228078/85 | 1985-10-14 | ||
| JP228083/1985 | 1985-10-14 | ||
| JP228082/85 | 1985-10-14 | ||
| JP228080/1985 | 1985-10-14 | ||
| JP228078/1985 | 1985-10-14 | ||
| JP228077/85 | 1985-10-14 | ||
| JP60228078A JPS6286166A (en) | 1985-10-14 | 1985-10-14 | Formation of thin film |
| JP60228083A JPS6289876A (en) | 1985-10-14 | 1985-10-14 | Formation of thin film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106620A Division CN1027549C (en) | 1985-10-14 | 1986-10-14 | Microwave enhanced CVD system and method using magnetic field |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1102034A true CN1102034A (en) | 1995-04-26 |
| CN1053229C CN1053229C (en) | 2000-06-07 |
Family
ID=27529825
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106620A Expired - Lifetime CN1027549C (en) | 1985-10-14 | 1986-10-14 | Microwave enhanced CVD system and method using magnetic field |
| CN94106741A Expired - Lifetime CN1053230C (en) | 1985-10-14 | 1994-06-21 | Microwave enhanced cvd system under magnetic field |
| CN94106740A Expired - Lifetime CN1053229C (en) | 1985-10-14 | 1994-06-21 | Microwave enhanced CVD system under magnetic field |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106620A Expired - Lifetime CN1027549C (en) | 1985-10-14 | 1986-10-14 | Microwave enhanced CVD system and method using magnetic field |
| CN94106741A Expired - Lifetime CN1053230C (en) | 1985-10-14 | 1994-06-21 | Microwave enhanced cvd system under magnetic field |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR920000591B1 (en) |
| CN (3) | CN1027549C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100530509C (en) * | 2003-09-08 | 2009-08-19 | 德国罗特·劳股份有限公司 | Electron cyclotron resonance (ECR) plasma source having a linear plasma discharge opening |
| CN113795610A (en) * | 2019-04-26 | 2021-12-14 | 朗姆研究公司 | High temperature heating of substrates in processing chambers |
| CN115679443A (en) * | 2021-12-02 | 2023-02-03 | 北京大学 | Photo-assisted metal organic compound chemical vapor deposition device and implementation method |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6853141B2 (en) * | 2002-05-22 | 2005-02-08 | Daniel J. Hoffman | Capacitively coupled plasma reactor with magnetic plasma control |
| JP4770029B2 (en) * | 2001-01-22 | 2011-09-07 | 株式会社Ｉｈｉ | Plasma CVD apparatus and solar cell manufacturing method |
| DE102006037144B4 (en) * | 2006-08-09 | 2010-05-20 | Roth & Rau Ag | ECR plasma source |
| CN102290313B (en) * | 2011-09-26 | 2013-06-05 | 中国科学院微电子研究所 | A non-metallic vacuum chamber structure |
| CN103602957A (en) * | 2013-11-07 | 2014-02-26 | 中山市创科科研技术服务有限公司 | Equipment for preparing alpha_SiH membrane |
| CN110396675B (en) * | 2019-07-10 | 2021-12-31 | 中国科学院电工研究所 | Preparation method of plasma enhanced chemical vapor deposition metal film |
-
1986
- 1986-10-14 CN CN86106620A patent/CN1027549C/en not_active Expired - Lifetime
- 1986-10-14 KR KR1019860008597A patent/KR920000591B1/en not_active Expired
-
1994
- 1994-06-21 CN CN94106741A patent/CN1053230C/en not_active Expired - Lifetime
- 1994-06-21 CN CN94106740A patent/CN1053229C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100530509C (en) * | 2003-09-08 | 2009-08-19 | 德国罗特·劳股份有限公司 | Electron cyclotron resonance (ECR) plasma source having a linear plasma discharge opening |
| CN113795610A (en) * | 2019-04-26 | 2021-12-14 | 朗姆研究公司 | High temperature heating of substrates in processing chambers |
| CN115679443A (en) * | 2021-12-02 | 2023-02-03 | 北京大学 | Photo-assisted metal organic compound chemical vapor deposition device and implementation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053230C (en) | 2000-06-07 |
| KR920000591B1 (en) | 1992-01-16 |
| KR870004497A (en) | 1987-05-09 |
| CN1098243A (en) | 1995-02-01 |
| CN86106620A (en) | 1987-07-08 |
| CN1053229C (en) | 2000-06-07 |
| CN1027549C (en) | 1995-02-01 |
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