CN102066925A - Method of measuring nitrogen atoms, device for measuring nitrogen atoms and plasma processing device - Google Patents
Method of measuring nitrogen atoms, device for measuring nitrogen atoms and plasma processing device Download PDFInfo
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Abstract
Provided is a method for measuring nitrogen atoms whereby nitrogen atom density is measured in real time at around atmospheric pressure. A method for measuring nitrogen atoms whereby nitrogen atom density is measured at around atmospheric pressure, comprises: a procedure of mixing a portion in a definite amount of a nitrogen atom-containing gas generated from a nitrogen atom source with a definite amount of nitrogen monoxide gas with a known concentration in the downstream of the above-described nitrogen atom source; a procedure of, after the completion of the reaction between the above-described nitrogen atom-containing gas and the above-described nitrogen monoxide gas mixed therewith, measuring the nitrogen monoxide density and the nitrogen dioxide density; and a procedure of calculating the nitrogen atom density with the use of the relation that the nitrogen atom density corresponds to the difference obtained by subtracting the sum of the nitrogen monoxide concentration measured above and the nitrogen dioxide concentration measured above from the known concentration of the nitrogen monoxide gas as described above.
Description
Technical field
The present invention relates near atmospheric pressure to measure nitrogen-atoms the nitrogen-atoms assay method, measure the nitrogen-atoms determinator of nitrogen-atoms and used its plasma processing apparatus.
Background technology
By carrying by the free radical of discharge generation and it contact with object, thereby formation, the surface of carrying out oxide film, nitride film etc. are cleaned, Cement Composite Treated by Plasma is widely-used in recent years at a distance for the what is called of sterilization etc.In addition, most Cement Composite Treated by Plasma are under reduced pressure worked, and do not need near the processing of atmospheric pressure of vacuum airtight container to receive publicity in recent years.Accompany with it, near the remote Cement Composite Treated by Plasma atmospheric pressure is used to the improvement, film forming of the cleaning of material surface, wetting state etc., and its application spreads all over a plurality of fields.On the other hand, by near the nitrogen atmospheric pressure discharge or used the discharge generation nitrogen free radical of the combination gas of nitrogen and rare gas, the gimmick etc. that forms nitride film by remote Cement Composite Treated by Plasma is also reported.
In nitrogen discharged remote Cement Composite Treated by Plasma, the main undertaker of reaction was electroneutral nitrogen free radical, particularly nitrogen-atoms, and the assurance of its density is important problem.But under near pressure high as the atmospheric pressure, the life-span of nitrogen-atoms is extremely short, significantly decays to a few tens of milliseconds with millisecond.Therefore, the mensuration difficulty of nitride atom density has adopted and has regulated discharged power, arrived the distance of processing object etc., finds the gimmick of optimal treatment condition on the experience.
But, since with the variation of discharge electrode temperature together, small pressure variation etc., nitride atom density changes significantly, therefore has the extremely difficult problem of supply under the stable density.If near atmospheric pressure, can enough easy methods measure nitride atom density in real time, then control discharging condition, the remote Cement Composite Treated by Plasma under optimal treatment condition becomes possibility.
As the typical example of in the past nitride atom density determination method, can enumerate the light of (1) irradiation specific wavelength, obtain the absorptionmetry (for example with reference to patent documentation 1) of nitride atom density by the decay of its light intensity; (2) under discharge, in gas, add nitrogen monoxide (below be designated as NO) gas, measure the nitrogen monoxide gas titrimetry (for example with reference to non-patent literature 1) of the luminous variation that the balance with NO amount of supplying with and nitrogen-atoms amount accompanies etc.
Below the nitrogen-atoms assay method of absorptionmetry is described.The nitride atom density assay method of absorptionmetry, the light by the atom light generating apparatus generation wavelength corresponding with the excitation level (for example wavelength 120nm) of nitrogen-atoms shines the gas that comprises nitrogen-atoms that becomes determination object.The light of irradiation is absorbed its light intensity decays according to the nitride atom density in the determination object gas.Therefore, the light intensity after passing through by preceding light intensity and determination object by the comparative measurements object can be calculated nitride atom density in real time.
Secondly, the nitrogen-atoms assay method to nitrogen monoxide gas titrimetry describes.If NO gas is mixed in the gas of nitrogen atom, because of the reaction of reaction equation (1) consumes NO.
N+NO→N
2+O(1)
Near being reflected at room temperature and the atmospheric pressure of reaction equation (1) extremely promptly carried out with about 1 millisecond and reached balance.The oxygen atom that produces in the reaction equation (1) (below be designated as the O atom) is according to the size of the amount of the amount of nitrogen-atoms and NO, by the reaction consumes of reaction equation (2) or reaction equation (3).
When the amount of nitrogen-atoms is bigger than the amount of NO,
O+N+M→NO(B
2∏)+M-→NO+M+h?v(2)
The amount of nitrogen-atoms is than the amount of NO hour,
O+NO+M→NO
2(A
2B
1)+M→NO
2+M+h?v (3)
In the zone (titration point) that the nitrogen-atoms amount equates with the NO amount, the passing that produces reaction equation (2), reaction equation (3), luminescence distribution changes.Therefore, by carry out luminous spectral photometry when the NO quantity delivered is changed, if find the titration point, then the supply NO amount thus the time can be calculated nitride atom density.
The prior art document
Patent documentation
Patent documentation 1: the spy opens the 2000-123996 communique
Non-patent literature
Non-patent literature 1:S.E.Babayan, outer 2, " Determination of theNitrogen Atom Density in the Afterglow of a Nitrogen andHelium; Nonequilibrium; Atmospheric Pressure Plasma ", PlasmaChemistry and Plasma Processing, the 21st volume, the 4th phase, Dec calendar year 2001,505-520 page or leaf
Summary of the invention
The problem that invention will solve
The nitride atom density assay method of absorptionmetry can carry out real-time nitride atom density to be measured, but generally is prerequisite with using under reduced pressure, is difficult to be applied to measure near the atmospheric pressure.This is because under near the high condition of particle density as the atmospheric pressure, the scattering of light of irradiation, decay become remarkable, diminish relatively as the absorption intensity of the nitrogen-atoms generation of determination object.
In addition, the nitride atom density assay method of nitrogen monoxide gas titrimetry can carry out near the more easy nitride atom density of atmospheric pressure and measure, and finds the titration point but be necessary to make the NO quantity delivered to change, and therefore can not realize The real time measure.
The object of the present invention is to provide near atmospheric pressure, measure nitride atom density in real time nitrogen-atoms assay method, used the nitrogen-atoms determinator of this nitrogen-atoms assay method and have the plasma processing apparatus of this nitrogen-atoms determinator.
Be used to solve the means of problem
The nitrogen-atoms assay method that the present invention relates to is near measure the density of nitrogen-atoms atmospheric pressure a nitrogen-atoms assay method, have: for the ormal weight in the gas that contains nitrogen-atoms that in nitrogen-atoms generation source, takes place, downstream in above-mentioned nitrogen-atoms generation source, the step of the nitrogen monoxide gas of the ormal weight that melting concn is known; After the reaction of the above-mentioned gas that contains nitrogen-atoms and the above-mentioned nitrogen monoxide gas that mixes, measure the step of the density of nitric oxide production density and nitrogen dioxide; Use nitride atom density to deduct the relation of the resulting difference of concentration sum of the above-mentioned nitrogen dioxide of the above-mentioned nitric oxide production concentration of mensuration and mensuration for known concentration, calculate the step of nitride atom density from above-mentioned nitrogen monoxide gas.
The nitrogen-atoms determinator that the present invention relates to is near measure the density of nitrogen-atoms atmospheric pressure a nitrogen-atoms determinator, have:, the air-breathing device in downstream in source takes place from above-mentioned nitrogen-atoms for the ormal weight in the gas that contains nitrogen-atoms that in nitrogen-atoms generation source, takes place; With the above-mentioned air-breathing gas regulation that contains nitrogen-atoms is the flow regulator of regulation flow; Supply with the nitrogen monoxide gas supply source of the known nitrogen monoxide gas of concentration; The nitrogen monoxide gas of above-mentioned supply is adjusted to the flow regulator of regulation flow; The tester of the density of nitric oxide production density of instrumentation and nitrogen dioxide, for the above-mentioned air-breathing gas that contains nitrogen-atoms, after mixing above-mentioned nitrogen monoxide gas, measure the density of nitric oxide production density and nitrogen dioxide, using nitride atom density simultaneously is the relation of the resulting difference of concentration sum that deducts the above-mentioned nitrogen dioxide of the above-mentioned nitric oxide production concentration of mensuration and mensuration from the known concentration of above-mentioned nitrogen monoxide gas, calculates nitride atom density.
The plasma processing apparatus that the present invention relates to is by making the gas that contains nitrogen-atoms contact the plasma processing apparatus of handling with process object, when having the nitrogen-atoms determinator that the present invention relates to, also have control discharged power, gas composition, gas flow, gas temperature, gaseous tension at least any so that above-mentioned nitride atom density is the control device of the density of regulation.
The effect of invention
The effect of the nitrogen-atoms assay method that the present invention relates to is, because nitrogen monoxide gas by the ormal weight that melting concn is known in containing the gas of nitrogen-atoms, mensuration makes gas and nitrogen monoxide behind the nitrogen monoxide solid/liquid/gas reactions and the nitrogen dioxide density separately that contains nitrogen-atoms, use known concentration and the nitrogen monoxide of mensuration and the density of nitrogen dioxide of the nitrogen monoxide gas that mixes, thereby obtain nitride atom density, therefore near atmospheric pressure, can carry out The real time measure nitride atom density.
Description of drawings
Fig. 1 is the block scheme of the formation of the expression nitrogen-atoms determinator of having used the nitrogen-atoms assay method that embodiments of the present invention 1 relate to.
Fig. 2 is expression to change the result's who carries out chemical simulation figure by the time of mixing each particle density that nitrogen monoxide produces in containing the discharge gas downstream of nitrogen-atoms.
Fig. 3 is expression from the nitrogen monoxide density of being obtained by chemical reaction simulation, nitride atom density that nitrogen dioxide density the is calculated figure with the comparison of the nitride atom density that uses as initial value.
Fig. 4 is the block scheme of the formation of the expression nitrogen-atoms determinator of having used the nitrogen-atoms assay method that embodiments of the present invention 2 relate to.
Fig. 5 is each condition and the measured data in the experimental example in the embodiments of the present invention 2.
Fig. 6 is an example of the measured result of the nitrogen-atoms attenuation characteristic in the embodiments of the present invention 2.
Fig. 7 is the block scheme of the formation of the plasma processing apparatus that relates to of expression embodiments of the present invention 3.
Description of reference numerals
Discharge cell, 4 high-voltage power supplies, 5 gas supply sources, 6 pumps, 7 nitrous oxides concentration meters, 8,8a, 8b, 8c gas mixing point, 9 gas inspiratory points, 10 delivery pipes, 11 are measured air shooter, 12a, 12b, 12c valve, 13 sequence controllers (sequencer), 14 process chambers near 1 nitrogen supply source, 2a, 2b, 2c flow regulator, 3 atmospheric pressure.
Embodiment
Embodiment 1.
In the explanation of following embodiment, use the number density (cm of souvenir [X] expression particle kind X
-3).On the other hand, in the NO mensuration etc., working concentration C
X(ppm) convenient.If pressure is designated as P (kPa), gas temperature is designated as T (K), number density [X] and concentration C
XThe relation of available formula (4) is changed mutually.N is arranged again
AExpression Avogadro constant number 6.02 * 10
23(mol
-1).
[X](cm
-3)＝N
A/22.4/1000×(P/101.3)×(273.1/T)×C
X×10
-6(4)
As required number density and concentration are changed.In addition, use souvenir [X]
InThe supply number density of expression particle kind X is used souvenir [X]
mThe number density of the mensuration of expression particle kind X.In addition, near the so-called atmospheric pressure, be the scope of absolute pressure 50kPa～200kPa.
Fig. 1 is the block scheme of the formation of the expression nitrogen-atoms determinator of using the nitrogen-atoms assay method that embodiments of the present invention 1 relate to.Below based on Fig. 1 embodiment 1 is described.
In the nitrogen-atoms determinator that embodiments of the present invention 1 relate to,, generate the gas that contains nitrogen-atoms, carry by delivery pipe 10 by nitrogen supply source 1, as near the discharge cell 3 flow regulator 2a of nitrogen flow regulating device, the atmospheric pressure.Wherein, the gas of supplying with pure nitrogen gas or nitrogen and rare gas being mixed from nitrogen supply source 1 with the ratio of regulation.
Bag pair of electrodes in the discharge cell 3 is connecting high-voltage power supply 4 near the atmospheric pressure.
Nitrogen-atoms instrumentation portion comprises NO gas supply source 5, as the flow regulator 2b of NO airshed regulating device, as the pump 6 of the air-breathing device of the part of the gas that will contain nitrogen-atoms, as the flow regulator 2c of the flow regulator of the gas that contains nitrogen-atoms, measure NO and NO
2The nitrous oxides concentration meter 7 of concentration.
From NO gas supply source 5, supplying with nitrogen or rare gas dilution is the NO gas of normal concentration.Gas inspiratory point 9 is positioned near the downstream of the discharge cell 3 of atmospheric pressure, at gas inspiratory point 9, measures air shooter 11 branches.NO gas mixing point 8 is present in measures air shooter 11, and flow regulator 2c and nitrous oxides concentration meter 7 all are positioned at the downstream of the NO gas mixing point 8 of measuring air shooter 11.
Secondly, the nitride atom density measuring principle is described.Nitrogen when the discharge space, the reaction of the main through type of nitrogen molecular (5) and be dissociated into nitrogen-atoms.
N
2+e-→2N+e(5)
Therefore nitrogen-atoms active high can be used for such various uses such as nitride film formation.On the other hand, nitrogen-atoms is under near pressure high as the atmospheric pressure, and the life-span is extremely short, with decay significantly about a few milli～a few tens of milliseconds.Problem of the present invention is to provide method and the determinator with the density of easy method and the short-life like this nitrogen-atoms of The real time measure.In addition, also be to provide its measuring method of use to carry out the plasma processing apparatus of High Accuracy Control.
The principle of measuring according to the nitride atom density of the present patent application is the known NO gas of hybrid density in the gas that contains nitrogen-atoms of density the unknown, and the reaction of mensuration nitrogen-atoms and NO reaches the composition density after the balance, thereby calculates nitride atom density.According to reaction equation (1), the nitrogen-atoms and the NO utmost point promptly react, and generate nitrogen molecular and O atom.Wherein the O atom of Chan Shenging further with reactions such as nitrogen-atoms, NO, generate other product.Like this, the reaction complexity that contains the mixed stocker of the gas of nitrogen-atoms and NO gas.But,, can calculate nitride atom density from NO density and the reacted composition density supplied with if know the nitride atom density as determination object, the NO density of supply and the relation between the back product density that generates of reaction.The present application people studies in great detail the reaction system of nitrogen-atoms and NO, found that the relation of formula (6) is set up.
[N]＝[NO]
in-([NO]
m+[NO
2]
m)(6)
Secondly, to describing until the process that finds formula (6).
In containing the gas of nitrogen-atoms, mixed under the situation of NO gas, between nitrogen-atoms, NO and diluents, produced various reactions, reached balance through behind the certain hour.By 14 reaction equations shown in consideration formula (7)～(20), the reaction when simulation has mixed NO gas in containing the gas of nitrogen-atoms compares the composition density before and after the reaction.Used EngineeringEqartion Solver (F-Chart Software) in the simulation.In addition, the velocity coefficient of each reaction is all quoted from the ChemicalKinetic Database of National Institute of Standards and technOlogy (NIST).Wherein, M means trisome, corresponding to all particle kinds that occur in the above-mentioned reaction system.
N+N+M→N
2+M?K
7＝1.22×10
-32(cm
6/s)(7)
N+O+M→NO+M?K
8＝9.80×10
-33(cm
6/s)(8)
N+O
2→NO+O?K
9＝1.11×10
-16(cm
3/s)(9)
N+O
3→NO+O
2?K
10＝1.00×10
-16(cm
3/s)(10)
N+NO→N
2+O?K
11＝2.94×10
-11(cm
3/s)(11)
N+NO
2→N
2O+O?K
12＝1.21×10
-11(cm
3/s)(12)
O+O+M-→O
2+M?K
13＝1.05×10
-33(cm
6/s)(13)
O+O
2+N→O
3+M?K
14＝5.88×10
-34(cm
6/s)(14)
O+O
3→O
2+O
2?K
15＝7.96×10
-15(cm
3/s)(15)
O+NO+M→NO
2+O
2?K
16＝8.84×10
-32(cm
6/s)(16)
O+NO
2→NO+O
2?K
17＝9.73×1O
-12(cm
3/s)(17)
O
2+NO+NO→NO
2+NO
2?K
18＝1.93×10
-38(cm
6/s)(18)
O
3+NO→O
2+NO
2?K
19＝1.82×10
-14(cm
3/s)(19)
O
3+NO
2→NO
3+O
2?K
20＝3.23×10
-17(cm
3/s)(20)
As initial stage density, for nitrogen-atoms [N]
0, nitrogen monoxide [NO]
0, nitrogen molecular [N
2]
0, give 5 * 10 respectively
14(cm
-3), 1 * 10
15(cm
-3), 2.5 * 10
19(cm
-3), all give 0 (cm for the material beyond it
-3), will carry out Simulation result and be shown in Fig. 2.The longitudinal axis is represented population density, and transverse axis represents to mix from NO gas the elapsed time of beginning.The moment that x=0 mixes with the gas that contains nitrogen-atoms corresponding to NO gas.
By the chemical reaction analog result of Fig. 2 as can be known, nitride atom density with the mixing of NO gas after sharply reduce, with about 1 millisecond, roughly bury in oblivion.In addition, the nitric oxide production density of supply more and more reduces, and produces nitrogen dioxide.
Wherein, to the density The effect of each composition before and after the reaction, found that the relation of formula (6) is set up.That is, be mixed in the gas that contains nitrogen-atoms NO behind the assaying reaction and NO by the NO gas that density is known
2Density, thereby can enough formulas (6) calculate nitride atom density.
In addition, this reaction reaches balance with about 1 millisecond utmost point short time, therefore can measure the nitride atom density of NO gas mixing point in fact.
In addition, according to Fig. 2, after the arrival balance, the density of each composition changes hardly, even so NO and NO
2Instrumentation need the time, can not become problem at nitride atom density aspect calculating yet.
In addition, if supply with the known NO of density, NO behind the assaying reaction and NO continuously
2Density, can calculate nitride atom density in real time by formula (6).
Secondly, the condition that formula (6) is set up describes.
The nitride atom density that the determination method of the present patent application contains with mensuration in the gas of nitrogen-atoms is a purpose, wherein, certain value is assumed to initial stage nitride atom density [N]
0, it is implemented the chemical reaction simulation as the initial stage condition.Obtain reacted NO and NO thus
2Density, calculate nitride atom density by formula (6).For the condition that this nitrogen-atoms measuring principle is set up, consistent with the nitride atom density of calculating by formula (6) as the nitride atom density that initial value gives.
Fig. 3 is as [N]
0Give 1 * 10
14(cm
-3), 3 * 10
14(cm
-3), 5 * 10
14(cm
-3) these 3 kinds of conditions, to each analog result of implementing respectively.The longitudinal axis of Fig. 3 is the nitride atom density that is calculated by formula (6), and transverse axis is an initial stage NO density, i.e. [NO] in.
From result shown in Figure 3 as can be known, at [NO]
InSurpassed [N]
0Condition under, consistent admirably by the nitride atom density that formula (6) is obtained with the nitride atom density that gives as the initial stage condition, therefore [N] and [N]
0Relation is about equally set up.
In addition as can be known, even this characteristic initial stage nitride atom density [N]
0Change, set up too.
By above result, the condition that is used for formula (6) establishment is [NO]
InSurpass [N].But, [NO]
InSignificantly surpass under the situation of [N], because the ratio of the NO that the reaction with nitrogen-atoms reduces reduces the NO density ([NO] of result's supply
In) with the NO density of measuring ([NO]
m) difference diminish.As an example, suppose [NO]
InBe [N] 100 times.At this moment, the NO's that consumes owing to the reaction with nitrogen-atoms cuts to close and becomes about 1%.If supposition NO and NO
2Error at measurment be 1%, the error of having used the nitride atom density of formula (6) to measure becomes about 100%.In fact, inevitable about 1% the error of present available most nitrous oxides concentration meters.Like this, if the error in considering to survey, as calculating the condition of nitride atom density, than [NO] by formula (6)
In/ [N] is greater than 1 and be appropriate less than 100.In addition, if make than [NO]
In/ [N] is about 2, can precision measure nitride atom density best.
Secondly, the scope to the nitride atom density that can be measured by formula (6) describes.
Now, NO and NO have been used under the situation of the general device that can access
2The mensuration precision be about 0.1ppm.Under atmospheric pressure, 0.1ppm is corresponding to 2.5 * 10
12(cm
-3) about density.Therefore, the following of being obtained by formula (6) of nitride atom density is limited to 1 * 10
12(cm
-3) about.
Secondly, use Fig. 1, the action of the nitrogen-atoms determinator that embodiments of the present invention 1 are related to describes.
The generating unit of the gas that contains nitrogen-atoms is described at first.
To the nitrogen supplied with from nitrogen supply source 1 or the mixed gas of nitrogen and rare gas, be adjusted to the flow of regulation with flow regulator 2a after, by near the discharge cell atmospheric pressure 3.At this moment, near atmospheric pressure in the discharge cell 3 between the pair of electrodes of bag by high-voltage power supply 4 applying high voltages, discharge is taken place.Nitrogen dissociates its part and becomes nitrogen-atoms when the discharge space.The gas that contains nitrogen-atoms of Fa Shenging flows out to delivery pipe 10 near the end of downstream side of the discharge cell atmospheric pressure 3 like this.
Secondly, the action to the nitride atom density determination part describes.
The part of the gas that contains nitrogen-atoms that will flow out near the end of downstream side of the discharge cell atmospheric pressure 3, air-breathing from gas inspiratory point 9 usefulness pumps 6.Air-breathing gas flow is regulated by flow regulator 2c.Under the air-breathing state of the part of the gas that will contain nitrogen-atoms, supply with the NO gas that is diluted to normal concentration from NO gas supply source 5.As diluents, use nitrogen or rare gas.If the concentration height of the NO that supplies with must make supply flow rate little, the result needs the time with mixing of the gas that contains nitrogen-atoms.On the other hand, if NO concentration is low, must make supply flow rate big, NO gas consumption increases.
In addition, by gas is mixed, will must implement after the mensuration to revise as the gas dilution that contains nitrogen-atoms of determination object.Usually, wish to use the NO about 1000ppm, but suitably determine according to flow as the nitride atom density of determination object, the inspiratory flow that contains the gas of nitrogen-atoms, NO gas.After the NO gas of supplying with is adjusted to the flow of regulation by flow regulator 2b, mix with the air-breathing gas that contains nitrogen-atoms at NO gas mixing point 8.At delivery pipe 10 with measure in the air shooter 11, nitride atom density is according to formula (7) and rapid attenuation near atmospheric pressure, decays to 1 * 10 after 1 second
12(cm
-3) about.Therefore, to be made as near the time of delivery of the end of downstream side of the discharge cell atmospheric pressure 3 be position below 1 second to NO gas mixing point 8.
Secondly, the nitrous oxides concentration meter 7 in the downstream by being arranged on NO gas mixing point 8 is measured NO and NO
2Concentration.As previously mentioned, before the chemical reaction in mixed gas reaches balance, near the time that has the atmospheric pressure about 1 millisecond.Therefore, nitrous oxides concentration meter 7 the position is set, consider air-breathing gas flow and NO airshed and pipe arrangement diameter, be made as the position that needs the time more than at least 1 millisecond from the conveying of NO gas mixing point 8.But, reach balance time,, also surpass 1 millisecond sometimes, therefore must consider these suitably positions of decision nitrous oxides concentration meter 7 because of the shape of gaseous tension, gas temperature, gas flow, pipe arrangement until chemical reaction.
If the concentration of the NO gas supplied with is made as C
NOO(ppm), flow is made as Q
NO(cm
3/ s), the air-breathing gas flow that contains nitrogen-atoms is made as Q
N(cm
3/ s), the NO concentration C at mixing point 8 places
NOi(ppm) obtain by formula (21).
C
NOi＝C
NO0×Q
N0/(Q
N0+Q
N)(21)
In addition, reacted NO concentration C
NomAnd NO
2Concentration C
NO2mMeasure by nitrous oxides concentration meter 7.Through type (4) is respectively with C
NOi, C
NOm, C
NO2mBe scaled number density, substitution formula (6) then can be calculated the target nitride atom density.Have, as shown in Figure 2, the reaction of nitrogen-atoms and NO is about 1 millisecond, is exceedingly fast again, and therefore NO gas mixing point 8 can be considered as the nitride atom density measuring point.
Like this, according to the embodiment of the present invention 1, the part of the gas by will containing nitrogen-atoms is air-breathing, mixes the NO of regulation density, NO behind the assaying reaction and NO
2Density, thus can use formula (6) near atmospheric pressure, to calculate nitride atom density in real time.
Have, by mix NO gas in containing the gas of nitrogen-atoms, will contain the gas dilution of nitrogen-atoms, nitride atom density reduces.Therefore, in order strictly to calculate nitride atom density, must implement to convert according to formula (22) to the nitride atom density of obtaining with formula (6).
[N]
R＝[N]
m×(Q
NO+Q
N)/Q
N(22)
Wherein, [N]
RFor having implemented the more accurate nitride atom density after the conversion, [N]
mBe the nitride atom density of obtaining by formula (6).For example, if the NO airshed is 1/10 of the air-breathing gas flow that contains nitrogen-atoms, at [N]
R[N]
mMiddle about 10% the difference that produces.Therefore, consider the ratio of gas flow, carry out the correction of formula (22) as required.
In the embodiments of the present invention 1, during taking place, used nitrogen-atoms near the discharge of atmospheric pressure.This be because, by near atmospheric pressure, forming nonequilibrium plasma, thereby generate the electronics of high energy, make the generation of dissociating of nitrogen molecular expeditiously.As near the example that the discharge form of nonequilibrium plasma can take place atmospheric pressure, can enumerate dielectric and intercept discharge, Atomospheric pressure glow discharge, creeping discharge, short pulse corona discharge etc.
On the other hand, the nitrogen-atoms determination method that the present invention relates to is even the nitrogen-atoms that takes place in any means also can be measured.Therefore, even beyond above-mentioned, for example by the nitrogen-atoms of thermal dissociation, electron beam irradiation generation, mensuration also can use the same method.
In addition, in the embodiments of the present invention 1, pump 6 is to contain the air-breathing device of a part of the gas of nitrogen-atoms.In addition, flow regulator 2c is a device of regulating the air-breathing gas flow that contains nitrogen-atoms.Even do not use them, the mechanism that also can enoughly can produce the flow of pressure differential, introducing regulation replaces.For example, if replace using pump and making delivery pipe 10 be pressurized state, replacement flow regulator 2c and use needle-valve can introduce the gas that contains nitrogen-atoms of required flow.
The nitrous oxides concentration meter 7 that uses in the embodiments of the present invention 1 is used to measure NO and NO
2Concentration, can use the densimeter of variety of ways such as chemiluminescence formula, zirconia formula, fixed electric potential electroanalysis formula.Beyond the nitrous oxides concentration meter, so long as can measure NO and NO
2The device of concentration, can substitute with any device.As an example, the infrared extinction photometer of Fourier transform type (FTIR), mass analyzer, gas chromatography etc. also can be used.
In the embodiments of the present invention 1, NO and NO have been measured independently with oxides of nitrogen meter 7
2Concentration, also can by measure as both and total nitrogen oxide concentration [NO
x]
m, obtain nitride atom density.At this moment, the available formula of formula (6) (23) is rewritten.
[N]＝[NO]
in-[NO
x]
m (23)
In the embodiments of the present invention 1, by the position of suitable setting gas mixing point 8, the nitride atom density when can the prediction processing object arriving.To be made as L to the distance of handling object from gas inspiratory point 9
1, the sectional area of delivery pipe 10 is made as S
1, gas flow is made as Q
1, the pressure in the pipe is made as P
1, gas temperature is made as T
1In addition, the distance from gas inspiratory point 9 to gas mixing point 8 is made as L
2, the sectional area of measuring air shooter 11 is made as S
2, gas flow is made as Q
2, will manage internal pressure and be made as P
2, gas temperature is made as T
2In addition, determine L according to formula (24)
2Thus, arrive the time of process object until the gas that contains nitrogen-atoms and arrive NO gas mixing point 8 until the gas that contains nitrogen-atoms, the time that is the nitride atom density measuring point becomes equal, and the nitride atom density the when nitride atom density of mensuration becomes and arrives with the process object thing equates.
L
2＝L
1×(Q
2×S
1×P
1×T
2)/(Q
1×S
2×P
2×T
1)(24)
Satisfy the system of formula (24) by use, can obtain the nitride atom density that arrives process object indirectly, effectively control and treatment time, treatment conditions.
In addition, in the embodiments of the present invention 1, will be air-breathing by the part of the gas that contains nitrogen-atoms of discharge generation, measure.On the other hand, only under the situation that is determined as purpose with nitride atom density, also can realize by directly mixing NO gas in the gas that contains nitrogen-atoms of circulation in delivery pipe 10.But, in this case, therefore nitrogen-atoms can not implement remote Cement Composite Treated by Plasma because of burying in oblivion with the reaction of NO.
Fig. 4 has used the block scheme of formation of the nitrogen-atoms determinator of the nitrogen-atoms assay method that embodiments of the present invention 2 relate to for expression.
The nitrogen-atoms determinator that embodiments of the present invention 2 relate to the nitrogen-atoms determinator that embodiments of the present invention 1 relate to, mixes the number difference at the position of NO gas, and is identical in addition, therefore the identical symbol of same part mark omitted explanation.
In the nitrogen-atoms determinator that embodiments of the present invention 1 relate to, NO gas is a bit mixing at NO gas mixing point 8 only, but in the nitrogen-atoms determinator that embodiments of the present invention 2 relate to, measure the NO gas mixing point 8a of air shooter 11,3 mixing of 8b, 8c on the edge.
And, will be used to switch NO gas and supply with valve 12a, 12b, the 12c of stream and be provided in respectively between flow regulator 2b and NO gas mixing point 8a, 8b, the 8c.
Secondly, the action of the nitrogen-atoms determinator that embodiments of the present invention 2 are related to describes.
Using pump 6, the gas that will contain nitrogen-atoms from gas inspiratory point 9 with the regulation flow air-breathing before, identical with embodiment 1.In the embodiment 2, at first shut-off valve 12b and valve 12c, a relief valve 12a supplies with NO gas.Measure the nitride atom density at NO gas mixing point 8a place thus.
Secondly, a relief valve 12b supplies with NO gas.Measure the nitride atom density at NO gas mixing point 8b place thus.
Secondly, a relief valve 12c supplies with NO gas.Measure the nitride atom density at NO gas mixing point 8c place thus.Thus, along the gas stream of measuring air shooter 11, measure 3 different nitride atom densities of locating.
On the other hand, by gas flow rate, distance, can calculate until the time that arrives NO gas mixing point, i.e. time of delivery near the end of downstream side of the discharge cell atmospheric pressure 3 to NO gas mixing point 8a, 8b, 8c.The nitride atom density of measuring is taken as the longitudinal axis, will be taken as the transverse axis mapping, thereby obtain the attenuation characteristic of nitride atom density until the time of delivery of measuring point.
Secondly, the concrete method that the nitrogen-atoms determinator that is used for relating to embodiments of the present invention 2 is obtained the attenuation characteristic of nitride atom density describes.The nitride atom density that NO gas mixing point 8a, 8b, 8c place are measured is designated as Na, Nb, Nc respectively, will be designated as Ta, Tb, Tc until the time of delivery of each NO gas mixing point 8a, 8b, 8c.Use these values, to the relation mapping of nitride atom density and time of delivery.On the other hand, as the attenuation process of nitrogen-atoms, during consideration formula (7), the theoretical formula of nitride atom density decay is formula (25).
[N]＝1/([M]k
rt+1/[N]
0)(25)
Wherein, k
r(cm
6/ s) be space recombination velocity coefficient.In addition, [M] is the density of trisome, calculated by pressure and temperature.
Nitride atom density Na, Nb, Nc and time of delivery Ta, Tb, Tc that use is measured from NO gas mixing point 8a, 8b, 8c mixing NO gas implement the regretional analysis for formula (25), thereby [N] in the formula of obtaining (25)
0And k
rWherein, [N]
0Nitride atom density near 3 exits of the discharge cell atmospheric pressure.
In addition, [N] by obtaining
0And k
rBe worth substitution formula (25), can access the relation of the time variation that gives nitride atom density.Can estimate measuring point nitride atom density in addition thus.
Secondly, one experimental example of the nitride atom density mensuration of the nitrogen-atoms assay method enforcement that relates to based on embodiments of the present invention 2 is shown.
The nitrogen of per minute 10 liters (10slm) is supplied near the discharge cell 3 of atmospheric pressure.Near atmospheric pressure in the discharge cell 3, the pair of electrodes of electrode gap 1mm, long 120mm is added ac high voltage, intercept discharge by the dielectric under the atmospheric pressure nitrogen-atoms is taken place.From high-voltage power supply 4, output frequency 4.5kHz, the about 6.5kV of impressed voltage
0-pAlternating voltage.
The gas that contains nitrogen-atoms that takes place by discharging is transported to the downstream with the stainless-steel tube of internal diameter 4.35mm.Use pump 6 and flow regulator 2c, the discharge gas downstream of 10slm total amount is air-breathing, introduce determination part.NO gas mixing point 8a, 8b, 8c lay respectively at 40mm, 100mm, 160mm downstream apart near the outlet of the discharge cell atmospheric pressure 3.To add in the discharge gas downstream with the NO gas of the concentration 1000ppm of nitrogen dilution flow with per minute 100～300cc.NO and NO
2Mensuration in use FTIR.
The NO and the NO of NO concentration and mensuration will be supplied with
2Concentration is scaled density respectively, is calculated the nitride atom density of each NO gas mixing point 8a, 8b, 8c by formula (6).
Fig. 5 is each condition and the measured data in the experimental example.
NO and NO
2Measured concentration be respectively about 10ppm, 2ppm, nitride atom density is 10
14(cm
-3) about.The nitrogen-atoms attenuation characteristic that will be obtained by the mensuration at 3 positions is shown in Fig. 6.Nitride atom density is shown in the longitudinal axis, will be shown in transverse axis until the time of delivery t of NO gas mixing point.By with the comparison of theoretical formula of decay, obtain the nitride atom density [N] of t=0
0=4.1 * 10
14(cm
-3), the recombination velocity coefficient k
r=9.2 * 10
-33(cm
6/ s).Wherein, making pressure is 101.3kPa, when making gas temperature be 323K, and [M]=2.3 * 10 in the formula (25)
19(cm
-3).With these value substitution formulas (25), the formula as the nitride atom density decay obtains formula (26).
[N]＝1/(2.1×10
-13t+2.4×10
-15)(26)
By formula (26), for example to obtain be 7.8 * 10 to the nitride atom density of t=50msec
13(cm
-3), it is 4.3 * 10 that the nitride atom density of t=100msec is obtained
13(cm
-3).Like this, measure the nitride atom density at a plurality of positions, obtain [N]
0And k
r, can estimate the nitride atom density in the place beyond the NO gas mixing point.
According to the embodiment of the present invention 2, can measure nitride atom density at a plurality of positions, obtain the attenuation characteristic of nitrogen-atoms by relation with time of delivery, estimate the nitride atom density in the place beyond the NO gas mixing point based on this.
In above-mentioned nitride atom density attenuation characteristic, only consider space combination again, do not comprise the surface again in conjunction with waiting other nitrogen-atoms to bury in oblivion process.Therefore, because of the material of delivery pipe, the difference of shape, must implement to revise to formula (25).Especially, if use tubule as delivery pipe, the surface influence of combination more relatively becomes big.
Have, in the embodiment 2, making NO gas mixing point is 3 positions again, so long as more than 2 positions, then can make to use the same method.
Fig. 7 is the block scheme of the formation of the plasma processing apparatus that relates to of expression embodiments of the present invention 3.
The plasma processing apparatus that embodiments of the present invention 3 relate to is the plasma processing apparatus that the downstream of the nitrogen-atoms determinator that relates in embodiments of the present invention 1 has disposed process chamber 14.
And, in the nitrogen-atoms determinator that embodiments of the present invention 1 relate to, have from nitrous oxides concentration meter 7 and collect measurement result, based on the sequence controller 13 of measurement result control nitrogen supply source 1, flow regulator 2a, high-voltage power supply 4 etc.
Front end at the delivery pipe 10 that extends near the outlet of the discharge cell atmospheric pressure 3 is connected with process chamber 14.And near the gas that contains nitrogen-atoms that discharge cell 3 generates atmospheric pressure is imported into process chamber 14 by delivery pipe 10, is used for handling.
Secondly, the action of the plasma processing apparatus that embodiments of the present invention 3 are related to describes.
At first, with the method shown in the embodiment 1, measure NO and NO with nitrous oxides concentration meter 7
2 Concentration.In sequence controller 13, accept the data measured with nitrous oxides concentration meter 7, carry out formula (6), also add the calculation of following formula (22) as required, calculate nitride atom density.
Then, sequence controller 13 is based on the nitride atom density of calculating, control nitrogen supply source 1, flow regulator 2a, high-voltage power supply 4, not shown pressure governor and temperature regulator.Thus, regulate any one or many persons of flow, discharged power, gas temperature, the pressure of composition, the nitrogen of near the nitrogen that discharge cell 3 is supplied with atmospheric pressure.Thus, be adjusted to the nitride atom density, the nitrogen-atoms flow that are fit to technology, the gas that will contain nitrogen-atoms supplies to process chamber 14.
3 plasma processing apparatus that relate to according to the embodiment of the present invention, by nitride atom density is measured in real time, control discharging condition according to measurement result, thereby the gas that can will contain nitrogen-atoms under the state of keeping required nitride atom density supplies to process chamber 14.
In addition, can make with the form of be fit to handling nitride atom density, nitrogen-atoms flow through the time change, realize technology with High Accuracy Control.
Nitride atom density is owing to the time rapid attenuation, therefore wish to make the outlet and the process chamber 14 of near the discharge cell 3 of atmospheric pressure approaching as far as possible.As previously mentioned, need more than 1 second if carry near atmospheric pressure the time, nitride atom density decays at least 1 * 10
12(cm
-3) about, carry out nitride film formation, the reduction of the efficient when other are handled.Therefore, process chamber 14 be arranged on the conveying of the gas that contains nitrogen-atoms be 1 second with interior, preferred 0.1 second with interior position.
In addition, for nitrogen-atoms being supplied to process chamber 14, must make from gas inspiratory point 9 air-breathing flows the least possible to determination part with high flow capacity.
On the other hand, the lower limit of air-breathing flow to determination part is by being used to measure NO and NO
2The decision of necessary flow, be generally about 1 liter of per minute.
Have again,, used sequence controller 13 as calculation in the embodiment 3 and control device.Even beyond the sequence controller, also can be by calculating nitride atom density based on the calculation of formula (6), so long as based on the nitride atom density of obtaining, the device that can control conditions such as aforesaid discharged power gets final product.
In addition, in sequence controller 13, have calculation apparatus and control device simultaneously, but can make them independent.
Claims (9)
1. nitrogen-atoms assay method, it is near atmospheric pressure, measure the density of nitrogen-atoms nitrogen-atoms assay method, it is characterized in that having following steps: for the ormal weight in the gas that contains nitrogen-atoms that in nitrogen-atoms generation source, takes place, downstream in above-mentioned nitrogen-atoms generation source, the nitrogen monoxide gas of the ormal weight that melting concn is known; After the reaction of the above-mentioned gas that contains nitrogen-atoms and the above-mentioned nitrogen monoxide gas that mixes, measure the density of nitric oxide production density and nitrogen dioxide; Use following relation to calculate nitride atom density: nitride atom density is resulting poor for the concentration sum of the above-mentioned nitrogen dioxide of the above-mentioned nitric oxide production concentration that deducts mensuration from the known concentration of above-mentioned nitrogen monoxide gas and mensuration.
2. the described nitrogen-atoms assay method of claim 1 is characterized in that, the nitride atom density in the above-mentioned gas that contains nitrogen-atoms is 1 * 10
12(cm
-3) more than.
3. claim 1 or 2 described nitrogen-atoms assay methods is characterized in that, the known concentration of above-mentioned nitrogen monoxide gas and the ratio of above-mentioned nitride atom density are greater than 1 and less than 100.
4. each described nitrogen-atoms assay method of claim 1-3 is characterized in that, it is below 1 second until the time that above-mentioned nitrogen monoxide gas mixes that the above-mentioned gas that contains nitrogen-atoms goes out the back from above-mentioned nitrogen-atoms generation source and course.
5. nitrogen-atoms determinator, it is near atmospheric pressure, measure the density of nitrogen-atoms nitrogen-atoms determinator, it is characterized in that having:, the air-breathing device in downstream in source takes place from above-mentioned nitrogen-atoms for the ormal weight in the gas that contains nitrogen-atoms that in nitrogen-atoms generation source, takes place; With the above-mentioned air-breathing gas regulation that contains nitrogen-atoms is the flow regulator of regulation flow; Supply with the nitrogen monoxide gas supply source of the known nitrogen monoxide gas of concentration; The nitrogen monoxide gas of above-mentioned supply is adjusted to the flow regulator of regulation flow; The tester of the density of nitric oxide production density of instrumentation and nitrogen dioxide, for the above-mentioned air-breathing gas that contains nitrogen-atoms, after mixing above-mentioned nitrogen monoxide gas, measure the density of nitric oxide production density and nitrogen dioxide, use following relation to calculate nitride atom density simultaneously: nitride atom density is resulting poor for the concentration sum of the above-mentioned nitrogen dioxide that deducts the above-mentioned nitric oxide production concentration of mensuration and mensuration from the known concentration of above-mentioned nitrogen monoxide gas.
6. the described nitrogen-atoms determinator of claim 5 is characterized in that, the nitride atom density in the above-mentioned gas that contains nitrogen-atoms is 1 * 10
12(cm
-3) more than.
7. claim 5 or 6 described nitrogen-atoms determinators is characterized in that, the known concentration of above-mentioned nitrogen monoxide gas and the ratio of above-mentioned nitride atom density are greater than 1 and less than 100.
8. each described nitrogen-atoms determinator of claim 5-7 is characterized in that, it is below 1 second until the time that above-mentioned nitrogen monoxide gas mixes that the above-mentioned gas that contains nitrogen-atoms goes out the back from above-mentioned nitrogen-atoms generation source and course.
9. plasma processing apparatus, be by making the gas that contains nitrogen-atoms contact the plasma processing apparatus of handling with process object, it is characterized in that, have each described nitrogen-atoms determinator of aforesaid right requirement 5-8, at least one that also has control discharged power, gas composition, gas flow, gas temperature, a gaseous tension is so that above-mentioned nitride atom density is the control device of regulation density.
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|---|---|---|---|---|
| JP2000123996A (en) * | 1998-10-16 | 2000-04-28 | Toshio Goto | Atomic radical measuring method and device |
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| JP2000123996A (en) * | 1998-10-16 | 2000-04-28 | Toshio Goto | Atomic radical measuring method and device |
| JP2004354055A (en) * | 2003-05-27 | 2004-12-16 | Toshio Goto | Atomic radical density measuring device |
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