CN1833473A - Plasma processing method and apparatus - Google Patents
Plasma processing method and apparatus Download PDFInfo
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- CN1833473A CN1833473A CN 200480022737 CN200480022737A CN1833473A CN 1833473 A CN1833473 A CN 1833473A CN 200480022737 CN200480022737 CN 200480022737 CN 200480022737 A CN200480022737 A CN 200480022737A CN 1833473 A CN1833473 A CN 1833473A
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Abstract
In a plasma processing, the range of a supply frequency to between electrodes is set such that a stable discharge and a high output efficiency can be achieved. [MEANS FOR SOLVING PROBLEMS] In a plasma processing apparatus, there are provided a secondary coil (22b) of a transformer (22) that boosts a power supply voltage; and an electrode circuit (1) comprising a pair of electrodes (11,12) opposed to each other. There is also provided a solid dielectric (13) on the opposing surface of at least one of the electrodes (11,12). The electrode circuit (1) constitutes an LC series resonant circuit comprising a leakage inductance of the secondary coil and a capacitance of the electrodes. The supply frequency to the electrode circuit (1) is set between the resonant frequency during non-discharging and the resonant frequency during a period when the spacing (10p) between the electrodes can be regarded as a conductor.
Description
Technical field
The present invention relates to a kind of for example near forming plasma by glow discharge etc. under atmospheric pressure (roughly normal pressure) environment, object being treateds such as semiconductor substrate are carried out surface-treated method and device.
Background technology
People have proposed various near carrying out plasma treatment method under the processing atmosphere of atmospheric pressure.In these methods, cause Atomospheric pressure glow discharge, carry out plasma handling gas to applying electric field between the pair of electrodes.Processing gas after this plasma is used on the object being treated of semiconductor substrate etc., carried out surface treatments such as film forming or etching.
For example, the patent documentation spy opens that flat 10-36537 communique put down in writing, and arranged opposite has pair of electrodes, is provided with solid dielectric in the opposed faces of at least one side's electrode.And, near under the atmospheric pressure, give between the electrode and apply impulse electric field, form glow discharge plasma.The frequency that is used for the preferred pulse of stable plasma treatment is in the scope of 0.5kHz～100kHz.
The patent documentation spy opens in the 2001-284099 communique, and as the condition that the kind that does not rely on atmosphere gas can be carried out glow discharge, the dielectric electrostatic capacitance that is capped on electrode and the ratio of frequency of supply are at 1400pF/ (m
2KHz) below.
The patent documentation spy opens in the flat 10-154598 communique, though the electric field strength between the regulation electrode is 0.1～10kV/mm, frequency is 0.5～100kHz etc., and these numerical value are limited to the situation that electric field is an impulse wave that applies, and can't be applied to continuous waves such as sine wave.
Give between the electrode and apply the power supply that electric field is used, in general, primary voltage is boosted, the secondary voltage after boosting is supplied to electrode by transformer.For example, voltage Vpp under the situation about 5kV, only carries out glow discharge between the peak value in rare gas atmosphere when distance between electrodes is 1mm, and the size of output itself is also insufficient.If the voltage Vpp between the peak value when distance between electrodes is 1mm is 10～20kV, even then in the atmosphere beyond the rare gas such as air or nitrogen, also can cause glow discharge.Frequency is fixed on guarantees to export stable numerical value (for example 10kHz).But the efficiency of supply of power is lower, can not get enough output.In addition, if surpassing 20kV, the voltage Vpp between the peak value then becomes arc discharge.
In the above-mentioned method in the past, though proposed the various concrete value conditions such as frequency that are used under atmospheric pressure environment roughly, causing glow discharge, but those numerical value only just have meaning in the waveform of electric field or the kind of processing gas etc. under the given situation, can't be general.And, do not consider the delivery efficiency of supply unit in some cases, loss is bigger.Can guarantee power supply efficient and the stability of output and then the higher disposal ability of object being treated correspondence, yet not establish the condition that can be suitable for versatility as yet from power supply.
Summary of the invention
The inventor In view of the foregoing, has carried out studying intensively, investigating.That is,, can consider the impedance in the space between the electrode and being connected in series at the electric capacity of the solid dielectric of the opposed faces setting of at least one side's electrode by the electrode structure that a pair of opposite electrode is formed.And, usually, between electrode structure and power supply, inserting transformer, the secondary coil of this transformer is connected with the electrode of hot side.Owing in transformer, there is a leakage inductance, therefore, just constitute the LC series resonant circuit as seen by it and electrode structure.As everyone knows, in the LC series resonant circuit, when power supply being driven, can make to be output as maximum with resonance frequency.On the other hand, in above-mentioned electrode structure, though can obtain the electric capacity of solid dielectric easily, the impedance in the space between the electrode is directly resolved it easily because of generation changes such as isoionic states.
Yet, if be in discharge condition not so the impedance in the space between the electrode also for constant.At this moment resonance frequency, if know rerum naturas such as handling gas dielectric constant, just can obtain by calculating so, certainly, even if actual measurement also can be obtained easily.
The impedance in consideration space between the electrode when emitting electricity reduces, and is little when then resonance frequency is than absence of discharge.
And then, if surpass the state that glow discharge becomes arc discharge, then because the space that can look between the electrode is a conductor, so all impedances of electrode structure, only consider the amount of the electric capacity of solid dielectric.At this moment resonance frequency can be obtained by calculating.And, be the equivalent electric circuit of conductor by adopting, thereby also can measure the space metathesis between the electrode.
So the result of study tour obtains following opinion.That is,, and in the scope between the resonance frequency when regarding the space between the electrode as conductor, then can access stable glow discharge if give the resonance frequency of energising frequency when absence of discharge of electrode.And in this scope, must exist can the high frequency of exporting.
The 1st feature of the present invention is following opinion.
A kind of plasma processing method, possesses telegraph circuit 1, it contains mutual pair of electrodes facing 11,12 and inductor 22b, employing is provided with the plasma treatment appts of solid dielectric 13 in the opposed faces of at least one side's electrode, space 10p between above-mentioned those electrodes imports and handles gas, carry out plasma treatment after giving above-mentioned telegraph circuit 1 power supply simultaneously
Will be to the frequency of supply fs of the telegraph circuit 1 when this is handled, the resonance frequency f when being set in absence of discharge
R1(following suitably be called " the 1st resonance frequency "), and the resonance frequency f when regarding the space between the above-mentioned electrode as conductor
R2Between (following suitably be called " the 2nd resonance frequency ").
Perhaps, a kind of plasma treatment appts, it carries out carrying out plasma treatment after the plasma to handling gas by the power supply from power supply 21, possesses:
Like this, can obtain stable discharge condition, and the frequency range that existence can be become the crest frequency of high delivery efficiency is set generally.
Here, preferred space 10p between above-mentioned electrode on one side causes discharge, on one side at above-mentioned the 1st resonance frequency f
R1With the 2nd resonance frequency f
R2Between the frequency of supply fs that gives telegraph circuit 1 is regulated, obtain the frequency f that electric current is a peak value
PEAK, frequency of supply fs is set in this crest frequency f
PEAKPerhaps processing is carried out in back near it.Like this, can obtain high delivery efficiency definitely.
Can be with above-mentioned pair of electrodes 11,12, as being connected in series of the capacitive component Cd that is full of space 10p between the electrode of handling gas, capacitive component Cp when the absence of discharge and solid dielectric 13, calculate above-mentioned the 1st resonance frequency f
R1And, also above-mentioned pair of electrodes 11,12 only as the capacitive component Cd of solid dielectric 13, can be calculated above-mentioned the 2nd resonance frequency f
R2
Replace above-mentioned calculating, also can be according to the power supply of giving above-mentioned telegraph circuit 1, give to apply the electric field of amplitude that deficiency causes the threshold value of discharge between the electrode, regulate this frequency of supply simultaneously, be the frequency of peak value with electric current, as above-mentioned the 1st resonance frequency f
R1And, also can not exist the state (circuit diagram on the right side of Fig. 3) of the space 10p between the electrode to regulate frequency of supply down making above-mentioned pair of electrodes 11,12 hold solid dielectric 13 and butt under the arm, be the frequency of peak value with electric current, as above-mentioned the 2nd resonance frequency f
R2
Preferred above-mentioned plasma treatment appts, the mode of giving above-mentioned telegraph circuit 1 according to the back power supply of being boosted by 22 pairs of voltages from power supply 21 of transformer constitutes above-mentioned inductor by the leakage inductance L of above-mentioned transformer 22.
By in inductor of forming by above-mentioned leakage inductance L and the capacitor formed by above-mentioned pair of electrodes 11,12, add inductor Lx in kind, Ly or capacitor Cx, Cy, thereby also can constitute above-mentioned telegraph circuit 1.Like this, scalable the 1st, the 2nd resonance frequency f
R1, f
R2, even, and the setting range of the frequency of supply fs of scalable when handling.
And the result that inventors study intensively is to distinguish the bias of the frequency of supply of the natural mode shape correspondence when discharging, and have certain relation between the stability of power efficiency and output.
That is, shown in the solid line of Figure 12, the natural mode shape f of (deduction) during with discharge
0Corresponding frequency of supply fs departs from the very large region R 3 of positive and negative both direction, and power supply efficient is very low, and does not almost have to change to be in flat condition for the value of frequency of supply fs.Here, adopt the ratio Vpp/V of peak value front end (ト ウ) the crest voltage Vpp of input voltage V and thermode 11, as the index of power supply efficient.Than flat site R3 more near natural mode shape f
0Among the constant regional R2 of one side, according to along with natural mode shape f
0Become big mode near Vpp/V and describe the gradient.At region R 2, R3, Vpp/V is relative, and frequency of supply fs can roughly determine uniquely.That is, Vpp/V is not change in time, is in stable state.
If be in more close natural mode shape f than sloping region R2
0The region R 1 of the constant scope of one side is rising when then Vpp/V is along with effluxion.But its rising degree is slower, may command.And then, if near natural mode shape f
0, and be in and contain natural mode shape f
0The region R 0 of constant scope, then Vpp/V moment rises, and becomes uncontrollable.The dotted line of Figure 12 represents that the discharge in slow variable domain R1 and the momentary variation region R 0 begins Vpp/V afterwards.This Vpp/V is at natural mode shape f
0The place is peak value.
Natural mode shape f
0, because of the state of discharge changes, though specific difficulty depends on the voltage that applies between the electrode 11,12 because of thinking basically, so can be according in the identical deductions such as experiment that apply under the voltage.
The 2nd feature of the present invention is based on that above-mentioned opinion forms.
A kind of plasma processing method, by giving the telegraph circuit that constitutes lc circuit 1 power supply, this lc circuit contains pair of electrodes 11,12 and inductor 22b, thereby applying for roughly normal pressure space 10p down between above-mentioned those electrodes to cause behind the electric field discharges and carries out plasma treatment, and its implementation comprises:
Infer operation, it is to the natural mode shape f of above-mentioned telegraph circuit 1 lc circuit of the roughly normal pressure space 10p between the above-mentioned electrode when discharging
0Infer in advance;
Set operation, it sets the frequency of supply fs that gives above-mentioned lc circuit 1, from above-mentioned deduction natural mode shape f
0Depart from;
The plasma treatment operation, thus it is by carrying out plasma treatment with the frequency f s power supply that sets.
Like this, just can provide the general establishing method of the scope of a kind of frequency of supply fs, the frequency of supply fs of this scope can improve power efficiency and guarantee stability simultaneously.
In the 2nd feature, atmosphere gas can be rare gas such as helium or argon, also can be the gas beyond the rare gas such as air or nitrogen.Giving the supply waveform of lc circuit 1, can be continuous waves such as sine wave or rectangular wave, can also be interrupted waes such as impulse wave.
Here, what is called is normal pressure (near atmospheric pressure) roughly, is meant 1.013 * 10
4～50.663 * 10
4The scope of Pa, preferred if consider the facilitation that pressure is adjusted or install the easy that constitutes, be 1.333 * 10
4～10.664 * 10
4Pa, more preferably 9.331 * 10
4～10.397 * 10
4Pa
At above-mentioned natural mode shape f
0The deduction operation in, after temporarily powering to above-mentioned lc circuit 1, not only the cut-out because of this power supply can make above-mentioned lc circuit 1 produce damped oscillation, and apply voltage mode about equally with setting in the plasma treatment operation for the voltage that applies between the electrode 11,12 according to making at initial stage of this damped oscillation, measure the frequency at the initial stage of this damped oscillation, can be with this measured value as above-mentioned deduction natural mode shape f
0(with reference to Figure 11).Like this, the natural mode shape in the time of can inferring discharge definitely.Above-mentioned temporary transient discharge can be an interrupted wae, also can be continuous wave.When interrupted wae was powered, ending of each the ripple key element by interrupted wae cut off above-mentioned power supply.Therefore, can be in 1 ripple key element of interrupted wae and between the stand-down between the ensuing ripple key element initial stage frequency to the damped oscillation that in above-mentioned lc circuit, produces measure.Between preferred stand-down, be the fully concentrated length of damping.When continuous wave is powered, this continuous wave is ended, the initial stage frequency of thereafter damped oscillation is measured.Each the ripple key element of above-mentioned interrupted wae or the waveform of continuous wave can have various selections, for example can be rectangular waves, also can be sinusoidal wave, can also be triangular waves.Interrupted wae also can be an impulse wave.
And, in the above-mentioned deduction operation, make on one side to the setting in voltage and the plasma treatment operation of applying between the above-mentioned electrode to apply voltage and scan frequency of supply about equally simultaneously, obtain in input and output than the frequency of putting greatly, with it as above-mentioned deduction natural mode shape f
0
In above-mentioned setting operation, preferably set frequency of supply fs and be, at least from above-mentioned deduction natural mode shape f
0Periphery, input and output depart from than the region R 0 of momentary variation.Like this, can prevent to export out of control.According to the one side of the stability of exporting, preferably set not only from above-mentioned deduction natural mode shape f
0The input and output of periphery than the zone that produces change in time, be above-mentioned momentary variation region R 0, but also depart from from variable domain R1 slowly.That is, preferably set in input and output than stable in time region R 2, R3.But, when the processing of short time, can be set in above-mentioned slow variable domain R1.
More preferably, in the above-mentioned plasma treatment operation, fs is set in frequency of supply, and input and output are than the sloping region R2 that stablizes and increase and decrease according to frequency of supply fs in time.More preferably, fs is set in frequency of supply, input and output than among stable region R 2, the R3 in time, with the border of the region R 0 of change in time, R1, be sloping region R2 and the slow border of variable domain R1.Like this, can guarantee that the stable while of exporting can improve power efficiency.
Giving the power supply of above-mentioned lc circuit 1, is to boost by the output voltage by 22 couples of converter 21a of transformer to carry out, and preferred above-mentioned transformer 22 constitutes the inductor composition 22b of above-mentioned lc circuit 1.
Converting direct current to interchange by converter 21a, and then by boosting by transformer 22, thereby give under the situation of above-mentioned lc circuit 1 power supply, with the voltage Vpp between the peak value between the above-mentioned electrode 11,12, with the ratio (Vpp/V) of above-mentioned DC input voitage V as above-mentioned " input and output than ", can adopt its parameter when carrying out above-mentioned deduction operation or setting operation.
As shown in figure 12, according to inventor's experiment, natural mode shape f is being inferred in departing from of frequency of supply fs
0Roughly ± 25% in scope (fs=0.75f
0～1.25f
0), be momentary variation region R 0, at scope (fs=0.5f roughly ± 25%～roughly ± 50%
0～0.75f
0, 1.25f
0～1.5f
0), for slow variable domain R1, at scope (fs=0.2f roughly ± 50%～roughly ± 80%
0～0.5f
0, 1.5f
0～1.8f
0), for input and output than stable sloping region R2, roughly ± scope (fs≤0.2f more than 80%
0, fs 〉=1.8f
0), be flat site R3.Therefore, out of control in the above-mentioned plasma treatment operation for what prevent from least to export, in setting operation, set frequency of supply fs and depart from deduction natural mode shape f
0Roughly ± more than 25%.In order to guarantee stability definitely, preferably set frequency of supply fs and depart from deduction natural mode shape f
0Roughly ± more than 50%.For stable and power efficiency is good, preferably set frequency of supply fs and inferring natural mode shape f
0Roughly ± 50% (fs=0.5f
0, 1.5f
0).
Replace inferring natural oscillation product f
0Is benchmark with input and output than (for example Vpp/V), also can set the frequency of supply fs when handling.For example, front travel, its make between the above-mentioned electrode 11,12 apply voltage with processing under normal pressure roughly the time setting apply after voltage equates, scanning frequency of supply fs obtains the relation of frequency of supply fs and input and output ratio in advance; Set operation, the frequency of supply fs when it will be handled is set in, and above-mentioned input and output are than in the scope of relative its maximum below given percentage (for example roughly 70%); With the plasma treatment operation, thereby it is by carrying out plasma treatment with the frequency f s power supply that sets.Like this, can avoid momentary variation region R 0 at least.
The present invention, owing to be not by corona discharge etc., but carry out plasma treatment by glow discharge, so preferred electrode, be the shape that forms the equality electric field.The discharge portion of preferred electrode (perhaps dielectric) is planar (below, should planar part be called " discharge face ").And the distance between the preferred pair of electrodes is constant (discharge face of pair of electrodes is parallel to each other).Like this, can prevent to cause arc discharge, the glow discharge of homogeneous is produced because of electric field is concentrated.Distance between the preferred discharge face is for 0.5mm, below the 20mm, more preferably below the above 7mm of 1mm.Discharge face can be a curved surface, but the bigger side of preferred curvature radius (more than the R=5mm), more preferably plane.And preferred discharge face is level and smooth (smooth).If it is not have convex-concave or projection, then, therefore preferred because spark is noticeable.As the electrode structure that satisfies these conditions, enumerate: make pair of plates shape electrode parallel opposed the parallel plate electrode type, have the roller concave electrodes type that the concave electrodes of cylinder concave surface forms, coaxial cylinders electrode type of forming for coaxial inside and outside pair of cylinders shape electrode etc. by roller shape (cylindric) electrode with along its side face.
Description of drawings
Fig. 1 is the execution mode of expression the present invention the 1st feature, the schematic circuit diagram of atmospheric plasma processing unit
Fig. 2 is the equivalent circuit diagram of the telegraph circuit of said apparatus.
Fig. 3 is a key diagram of measuring the method for the 2nd resonance frequency in the said apparatus.
Fig. 4 is the circuit diagram of the variation of the telegraph circuit of expression said apparatus.
Fig. 5 is the circuit diagram of other variation of the telegraph circuit of expression said apparatus.
Fig. 6 is the curve chart of the measurement result of the relation of the expression frequency of the 1st embodiment and electric current.
Fig. 7 is the curve chart of the measurement result of the relation of the expression output of the 1st embodiment and isoionic luminous intensity.
Fig. 8 is the curve chart of the measurement result of the relation of the expression treatment conditions of the 1st embodiment and disposal ability (contact angle of every kind of propagation velocity).
Fig. 9 is the curve chart of the measurement result of the relation of the expression treatment conditions of the 3rd embodiment and disposal ability (contact angle of every kind of propagation velocity).
Figure 10 is the execution mode of expression the present invention the 2nd feature, the schematic circuit diagram of atmospheric plasma processing unit.
Figure 11 is used for inferring the converter output voltage V 1 of natural mode shape of device of Figure 10 and the wavy curve figure of electrode voltage V2 with the damped wave formula.
The curve chart of the relation of the input and output ratio of the frequency of supply correspondence when Figure 12 discharges for expression.
Among the figure: 1-telegraph circuit (lc circuit), 10-electrode structure, the space between the 10p-electrode, the 11-thermode, 12-grounding electrode, 13-solid dielectric, 20-electric field bringing device (supply unit), 21-alternating source, 21a-converter, the 22-transformer, 22a-primary winding, 22b-secondary coil (inductor), 23-frequency setting portion, Lx, Ly-inductor in kind, Cx, Cy-capacitor in kind, the fs-frequency of supply, f
PEAK-crest frequency, f
R1-Di 1 resonance frequency, f
R2-Di 2 resonance frequencys, f
0-infer natural frequency, R0-momentary variation zone, the slow variable domain of R1-, R2-steady gradient zone, R3-stablizes flat site.
Embodiment
Below, with reference to accompanying drawing, embodiments of the present invention are described.
(execution mode of relevant above-mentioned the 1st feature)
Shown in Fig. 1 pattern ground, the atmospheric plasma processing unit possesses electrode structure 10 and electric field bringing device (supply unit) 20.Electrode structure 10 is made of mutual pair of electrodes facing 11,12.In pair of electrodes 11,12, at least one side's the opposed faces, be provided with solid dielectric 13.Here,, also can be arranged on the thermode 11, also can be arranged on both sides' the electrode 11,12 though only be arranged on the grounding electrode 12.Space 10p between these electrodes 11,12 (between the solid dielectric 13 of thermode 11 and grounding electrode 12) imports processing gas by not shown processing gas introduction part.
Electric field bringing device 20 has alternating source 21 and transformer 22.Alternating source 21 for example has industrial alternating voltage is carried out becoming the rectification part of direct voltage and this direct voltage being changed the converter (with reference to the symbol 21a of Figure 10) that the alternating voltage of expected frequency is exported in the back after the rectification.The converter of alternating source 21 is connected with frequency setting portion 23, just can set adjusting promptly for the frequency of supply fs of telegraph circuit 1 power supply to the output frequency of alternating voltage by this frequency setting portion 23.In addition, output can be continuous waves such as sine wave, also can be interrupted waes such as impulse wave.
Like this, cause glow discharge after applying alternating electric field for space 10p between the electrode, the processing gas from above-mentioned processing gas introduction part is carried out plasma (containing activate, ionization etc.).By the processing gas after this plasma being used on the object being treateds such as semiconductor substrate, to impose the surface treatment of object being treated.In addition, this processing is being carried out near under the atmospheric pressure (roughly normal pressure).
By the secondary coil 22b and the electrode structure 10 of transformer 22, constitute telegraph circuit 1.In transformer 22, there is leakage inductance L.And, regard electrode structure 10 as capacitor.Therefore, telegraph circuit 1 can be considered to the LC series resonant circuit.Its resonance frequency f
r, be expressed from the next.
Here, L is the leakage inductance of coil 22b, and C is the electric capacity of electrode structure 10.
Fig. 2 is the equivalent electric circuit of telegraph circuit 1.Electrode structure 10 is by the impedance composition Zp of the space 10p between the electrode and being connected in series of capacitive component Cd of solid dielectric 13 are constituted.The impedance composition Zp of space 10p between electrode is by the capacitor C p of the space 10p between this electrode and the expression that is connected in parallel of resistance R.The capacitor C d of solid dielectric 13 by thickness and the area of section equidimension shape or the dielectric constant decision of this solid dielectric 13, can calculate easily.
When the space 10p between electrode does not produce discharge (during absence of discharge), in equivalent electric circuit, R=∞.Therefore, the capacitor C (=C of electrode structure 10
1), as follows:
The capacitor C p of space 10p between electrode during absence of discharge based on the thickness of this space 10p and area of section equidimension shape, also have the rerum naturas such as processing gas dielectric constant that are full of in the 10p of this space, can calculate easily.Perhaps, according to formula (2), the capacitor C in the time of can calculating absence of discharge easily
1
And, the resonance frequency f of the telegraph circuit 1 when absence of discharge
r(=f
R1), be expressed from the next.
According to above-mentioned formula (1a), (2), the resonance frequency f of the telegraph circuit 1 in the time of can easily calculating absence of discharge
R1Below, the resonance frequency f during with absence of discharge
R1Suitably be called " the 1st resonance frequency f
R1".
On the other hand, when the space 10p between electrode is just producing arc discharge, then can regard the space 10p between the electrode as conductor.At this moment, in the equivalent electric circuit of Fig. 2, R=0.Therefore, the capacitor C (=C of electrode structure 10
2) be
C
2=Cd (formula 3)
And, the resonance frequency f of the telegraph circuit 1 during arc discharge
r(=f
R2), be expressed from the next.
According to these formulas (1b), (3), the resonance frequency f of the telegraph circuit 1 in the time of can easily calculating arc discharge
R2Below, the resonance frequency f of (when regarding the space 10p between the electrode as conductor) during with arc discharge
R2Suitably be called " the 2nd resonance frequency f
R2".The 2nd resonance frequency f
R2, than the 1st resonance frequency f
R1Little.That is,
f
R2＜f
R1(formula 4)
In addition, the 1st, the 2nd resonance frequency f
R1, f
R2Even actual measurement also can be obtained.That is, such according to the electric field of the amplitude that applies the not enough threshold value that produces discharge between electrode 11,12, set the output voltage of alternating source 21.And, scanning output frequency, the electric current of the primary side (perhaps primary side) of mensuration transformer 22.This amperometric determination value is the frequency of peak value, is the 1st resonance frequency f
R1(with reference to Fig. 6).
And, as shown in Figure 3,, hold the electrode structure 10X that solid dielectric 13 makes it butt and do not have the space 10p between the electrode under the arm thereby make by amount of thickness with the space 10p between the only close electrode of pair of electrodes 11,12.Thus, can and arc discharge state (state of the space 10p between the electrode being regarded as conductor) on circuit the equivalence.And with above-mentioned same, the scanning output frequency carries out amperometric determination.This amperometric determination value is the frequency of peak value, is the 2nd resonance frequency f
R2(with reference to Fig. 6).
By plasma treatment appts when carrying out Surface Treatment with Plasma, by frequency setting portion 23, regulate promptly for the size of the frequency of supply fs of telegraph circuit 1 power supply to the output frequency of alternating source 21, make it by aforementioned calculation or measure resulting the 1st, the 2nd resonance frequency f
R1, f
R2Between.That is, adjusting makes it in the scope of following formula.
f
R2＜fs＜f
R1(formula 5)
Like this, the space 10p between electrode can produce stable glow discharge, can carry out good Surface Treatment with Plasma.
And in the scope that satisfies formula (5), must have delivery efficiency is the frequency f of peak value
PEAK(with reference to Fig. 6).That is, set up the relation of following formula.
f
R2＜f
PEAK＜f
R1(formula 6)
By frequency of supply fs being set at this peak value f
PEAKThereby, can access extremely good delivery efficiency.In addition, because space 10p between electrode then also can go down in the reaction on the surface of object being treated if reaction is carried out excessively, therefore under the sort of situation, can set frequency of supply fs and depart from from peak value.
The upper and lower bound of frequency of supply fs, i.e. the 1st, the 2nd resonance frequency f
R2, f
R2Value, can change arbitrarily.For example, as shown in Figure 4, at the leading portion or the back segment of the electrode structure 10 of telegraph circuit 1, inductor Lx in kind or capacitor Cx in kind are inserted in series connection; Perhaps as shown in Figure 5, be provided with inductor Ly in kind or capacitor Cy in kind is in parallel with electrode structure 10.Like this, can make the 1st, the 2nd resonance frequency f
R1, f
R2Depart from, even can change the frequency setting scope.Certainly, the variation of telegraph circuit 1 is not limited to Fig. 4, shown in Figure 5, can also adopt the circuit of a lot of forms to constitute.
Frequency setting scope shown in the above-mentioned formula (5) does not rely on the kind or the contents processing of output waveform or processing gas or installs formation etc., can use with versatility.That is, output waveform can be that impulse wave also can be that sinusoidal film can also be a rectangular wave.And, be widely used in film forming, etching, clean, various Surface Treatment with Plasma such as ashing, surface modification, handle the kind of gas or device and constitute and also not being defined.Can be applied to object being treated is configured in the so-called distance type of the outside of the space 10p between the electrode, and object being treated is configured in any mode of the so-called direct-type of the 10p inside, space between the electrode.In addition, be not limited to be applied to the plasma treatment that reduces pressure handling near the atmospheric plasma that carries out under the atmospheric pressure.
(the 1st embodiment)
The inventor, with the same plasma treatment appts of Fig. 1 in, with the method for above-mentioned execution mode to the 1st, the 2nd resonance frequency f
R1, f
R2Carry out actual measurement.That is, making the output voltage of power supply 21 is 50V, makes electric field between the electrode 11,12 be lower than the threshold value of discharge.Afterwards frequency is scanned, when the electric current of the primary side of transformer 22 is measured, shown in the chain-dotted line of Fig. 6, at 65kHz (=f roughly
R1) locate to occur the peak value of electric current.
And, make 2 electrodes, 11,12 butts as shown in Figure 3, when carrying out amperometric determination, shown in two chain-dotted lines of Fig. 6, at 20kHz (=f roughly
R2) locate to occur the peak value of electric current.
In addition, the current value of Fig. 6, the current value of representing as 100 standardization for the maximum during each is measured (with aftermentioned Fig. 7 too).And, obtaining resonance frequency f
R1, f
R2The current value in stage, even also faint at the peak value place, the current value when handling with glow discharge described later is compared quite little.
Thereafter, on one side space 10p between electrode import 100% nitrogen as handling gas, making the voltage of power supply 21 on one side is 250V, gives between the electrode 11,12 and applies alternating electric field.Then, measure the relation of frequency and electric current.Its result is, shown in the solid line of Fig. 6, at 55kHz (=f
PEAK) locate, the peak value of electric current appears.Thus, confirm to set up the relational expression f shown in the above-mentioned formula (6)
R2＜f
PEAK＜f
R1In addition, the primary side electric current when fs=55kHz is 9.2A, drops into power and promptly is output as 2300W.Converting if press each unit are of electrode, then is 12W/cm
2
And, as shown in Figure 7, confirm that the luminous intensity of discharge and output become big pro rata, work as f
PEAKDuring=55kHz, be maximum, extremely good and stable glow discharge.
At the relational expression f that sets up as the formula (5)
R2＜fs＜f
R1The scope of 20kHz～65kHz in, the whole zone of the space 10p between electrode can access stable discharge.At 65kHz (=f
1) above and 20kHz (=f
2) below, the discharge that obtains expecting is very difficult.
In addition, relatively at output 2500W, the condition of frequency 55kHz (A) and its be 1/2 output 1200W roughly, under the condition of frequency 30kHz (B), and the clean ability of gas (contact angle and propagation velocity).The propagation velocity of gas is 1m/min and 2m/min2 kind.And, under condition (A),, under condition (B), apply impulse electric field for the alternating electric field that applies from DC converting.Its result is, as shown in Figure 8, affirmation condition (A) is equal contact angle with the propagation velocity of 2 times of relative conditons (B), and disposal ability is roughly proportional with output.
(the 2nd embodiment)
Adopt and the identical device of above-mentioned the 1st embodiment, replace handling gas, during the concerning of mensuration frequency and electric current, obtain the result roughly the same with Fig. 6 with argon.At the f that sets up relational expression as the formula (5)
R2＜fs＜f
R1The scope of 20kHz～65kHz in, the whole zone of the space 10p between electrode can access stable discharge.If below 20kHz, improve output, then transit to sparkover.More than 65kHz, the then instantaneous arc discharge that transits to can't stable discharging.
(the 3rd embodiment)
At the 1st resonance frequency f
R1=190kHz, the 2nd resonance frequency f
R2In the device of=75kHz, adopt nitrogen, measure frequency f equally with above-mentioned the 1st embodiment as handling gas
PEAKIts result is to confirm f
PEAK=150kHz sets up the relational expression f shown in above-mentioned formula (6)
R2＜f
PEAK＜f
R1It more than 190kHz needle-discharging.Below 75kHz, can not produce discharge.
In addition, relatively at output 2000W, frequency 150kHz, from the condition (C) of the alternating electric field of DC converting and above-mentioned output 1/2 output 1200W roughly, frequency 30kHz, under the condition of impulse electric field (D), the clean ability of gas (contact angle and propagation velocity).Its result is, confirms as shown in Figure 9, and condition (C) is equal contact angle with the propagation velocity of 2 times of relative conditons (D), and disposal ability is roughly proportional with output.
(execution mode of relevant above-mentioned the 2nd feature)
The execution mode of the 2nd feature then, is described.About the formation that repeats with above-mentioned the 1st execution mode, additional prosign takes the circumstances into consideration to omit explanation.
As shown in figure 10, the electrode 11,12 of the atmospheric plasma processing unit of present embodiment is configured in the atmospheric air atmosphere.Atmosphere gas replaces air, also can be nitrogen, can also be rare gas such as helium or argon.Space 10p between electrode 11,12 imports processing gas by not shown processing gas introduction part.The thickness of space 10p between the electrode is for example 1mm.The opposed faces of at least one side in pair of electrodes 11,12 is provided with solid dielectric 13, omits its diagram.
Supply unit (electric field bringing device) 20 has converter 21a and transformer 22.Converter 21a is transformed into interchange after direct voltage V changed.
As above-mentioned the 1st execution mode was illustrated, the telegraph circuit 1 by the secondary coil 22b (leakage inductance L) and the electrode 11,12 (capacitor) of transformer 22 are formed constituted the LC series resonant circuit.
Though the electricity of the space 10p between the electrode is led, be zero when absence of discharge, when discharge for representing beyond zero and value that change because of discharge condition.Therefore, telegraph circuit 1 is the natural mode shape of lc circuit when discharge, because of the discharge condition difference.
On the other hand, discharge condition is basically because of changing for the voltage that applies that applies between the electrode.Therefore, the natural mode shape when thinking discharge depends on and applies voltage.
Below in the atmospheric plasma processing unit of above-mentioned formation, the process that is set in the frequency of supply fs that gives telegraph circuit 1 power supply when handling describes.
(the deduction operation of natural mode shape)
In the plasma treatment of reality (below be called " this processing ") before, infer telegraph circuit 1 natural mode shape f of (during discharge) when this processing in advance
0As presuming method, for example ensuing scan-type, damped wave formula etc. are arranged.
(the deduction method of scan-type)
On one side according to will give that electrode 11 applies apply voltage and maintain this processing the time the mode of size (Vpp=10kV) the input voltage V of converter 21a is regulated, one side is scanned frequency of supply fs in the scope of 0～hundreds of kHz.And, calculate input and output according to the regulated value of voltage V and compare Vpp/V.Thus, can access as shown in figure 12 data.And, the frequency f with input and output when very bigger than Vpp/V
0Be inferred as the natural mode shape of telegraph circuit 1.In this scan-type, notice that Vpp/V is promptly out of control in the output of momentary variation region R 0 near the peak value.
(the deduction method of damped wave formula)
As shown in figure 11, from converter 21a to transformer 22 incoming frequency f
1Wavy voltage V at intermittence
1This interrupted wae V
1Each ripple key element, be short period (1/f
1A) rectangular wave.The amplitude of each ripple key element is by the input voltage V decision of converter 21a.By this interrupted wae voltage V
1Power supply make and produce oscillating voltage V in the electrode 11 of telegraph circuit 1
2This voltage V
2, at above-mentioned interrupted wae voltage V
1Each ripple key element just be output during in, produce vibration with the frequency identical with this ripple key element.On the other hand, be in the moment that ends, voltage V from the ripple key element
2, carry out damping when producing vibration with vibration number intrinsic in the telegraph circuit 1.According to the voltage V between the peak value at initial stage of this damped oscillation
2Pp, the voltage Vpp between the peak value during with above-mentioned processing (=10kV) equate to set above-mentioned interrupted wae V like that
1The amplitude of each ripple key element be the input voltage V of converter 21a.
Like this, at the initial stage at least of damped oscillation, same discharge condition in the time of can making space 10p between the electrode be in, identical natural oscillation number in the time of can becoming with this processing with this processing.To initial stage of this damped oscillation, the 1st wave frequency f especially
0Measure.That is, to from interrupted wae V
1The ripple key element be in the voltage V that moment of ending begins
2(cycle: 1/f time of 1 internal circulating load
0) measure.Natural mode shape f when it is inferred as this processing
0
Preferred said determination is at each interrupted wae V
1The ripple key element be in by the time repeat, get its mean value.Like this, the deduction precision is improved.Preferred interrupted wae V
11 ripple key element and t between the stand-down between the ensuing ripple key element
1(=(1/f
1)-(1/f
1A)), be set at the very concentrated degree of damping.Like this, can avoid overlapping with ensuing damped wave.
Infer natural mode shape f
0, be for example 100kHz to 120kHz.
(setting operation)
Then, based on above-mentioned deduction natural mode shape f
0Frequency of supply fs when setting this processing.Most preferably, according to becoming above-mentioned deduction natural mode shape f
0± mode of 50% size sets.That is, be set at
Fs=f
0* (1-0.5)=0.5f
0(formula 7)
Perhaps fs=f
0* (1+0.5)=1.5f
0(formula 8)
This be in steady gradient region R 2 with the frequency on the border of variable domain R1.For example, at f
0During=120kHz, fs=60kHz.
And, in this treatment process, with setpoint frequency fs power supply simultaneously carry out atmospheric plasma processing on one side.Output stabilization can be made like this, and power efficiency can be improved.
In addition, as shown in figure 12, according to the viewpoint of the stability of exporting, frequency of supply fs is not limited to infer natural mode shape f
0Just ± 50%, also can deviate to more than it.That is, as long as in stability region R2, the R3 shown in the following formula 9,10.
Fs≤f
0* (1-0.5)=0.5f
0(formula 9)
Perhaps fs 〉=f
0* (1+0.5)=1.5f
0(formula 10)
But, the scope that preferably departs from, terminate in ± about 80%.Then power efficiency is low excessively more than it if deviate to, and it is difficult that the output that obtains expecting becomes.That is, shown in 11,12, remove the flat site R3 in the stability region.
Fs 〉=f
0* (1-0.8)=0.2f
0(formula 11)
Perhaps fs≤f
0* (1+0.8)=1.8f
0(formula 12)
If composite type 9～12, then can guarantee the stability exported, and the setting range of the power efficiency frequency of supply fs that also can work, for by the steady gradient region R 2 shown in the following formula 13,14.
0.2f
0≤ fs≤0.5f
0(formula 13)
Perhaps 1.5f
0≤ fs≤1.8f
0(formula 14)
And, when the processing time short (for example several branches～about 10 minutes), as long as make frequency of supply fs infer natural mode shape f relatively
0At least depart from ± get final product more than 25%, also can be set in ratio ± 50% near inferring natural mode shape f
0Side.That is, can be set in the slow variable domain R1 shown in the following formula 15,16.
0.5f
0＜fs≤0.75f
0(=f
0* (1-0.25)) ... (formula 15)
Perhaps 1.5f
0＞fs 〉=1.25f
0(=f
0* (1+0.25)) ... (formula 16)
In this slow variable domain R1, power efficiency is very high, can be exported greatly.Input and output are risen than passing through in time, but its degree is slow, can instantaneously not rise.Therefore, if end process and being in is ended at short notice, converter 21a or electrode 11 just can be damaged.
It is intrinsic by frequency of supply fs is inferred relatively at frequency f
0Depart from least ± more than 25%, thus input and output can be avoided the region R 0 (0.75f of momentary variation
0＜fs＜1.25f
0), can prevent to cause the element of converter 21a or electrode 11,12 destroyed because of big electric current.
As mentioned above, though to infer natural mode shape f
0Be benchmark, but can input and output be that benchmark replaces it also, set frequency of supply fs than Vpp/V.
If describe in detail, then at first,, obtain frequency of supply fs and the relation of input and output in advance than Vpp/V as front travel.Its method is identical in fact with above-mentioned " scan-type ".That is, on one side according to will give that electrode 11 applies apply voltage and maintain this processing the time the mode of size (Vpp=10kV) the primary side voltage V of converter 21a is regulated, the while is scanned frequency of supply fs in the scope of 0～hundreds of kHz.And V measures to voltage, and the input and output of calculating frequency of supply fs correspondence are than Vpp/V and datumization.
Then, as setting operation, above-mentioned input and output than Vpp/V relative its maximum for example 70% or following scope in frequency of supply fs when setting this processing.Like this, momentary variation region R 0 can be avoided at least, the destruction of electrode 11,12 or converter 21a can be prevented.
Utilize possibility on the industry
The present invention for example can be used in semi-conductive manufacturing process, the cleaning of semiconductor substrate, In the process for treating surface such as film forming (CVD), etching.
Claims (22)
1, a kind of plasma processing method, possesses the telegraph circuit that comprises mutual pair of electrodes facing and inductor, employing is provided with the plasma treatment appts of solid dielectric in the opposed faces of at least one side's electrode, import processing gas in described electrode space each other, carry out plasma treatment after giving described telegraph circuit power supply simultaneously, it is characterized in that
To when handling, this give the frequency of supply of telegraph circuit, resonance frequency when being set in absence of discharge (below be called " the 1st resonance frequency "), and between the resonance frequency when regarding the space between the described electrode as conductor (below be called " the 2nd resonance frequency ").
2, plasma processing method according to claim 1 is characterized in that,
The space of limit between described electrode causes discharge, the limit is regulated the frequency of supply of giving telegraph circuit between described the 1st resonance frequency and the 2nd resonance frequency, obtain the frequency that electric current is a peak value, frequency of supply is set at this crest frequency or near execution processing in back it.
3, plasma processing method according to claim 1 is characterized in that,
With described pair of electrodes,, calculate described the 1st resonance frequency as being connected in series of the capacitive component that is full of the capacitive component of handling the space between electrode gas, during absence of discharge and solid dielectric.
4, plasma processing method according to claim 1 is characterized in that,
With described pair of electrodes,, calculate described the 2nd resonance frequency only as the capacitive component of solid dielectric.
5, plasma processing method according to claim 1 is characterized in that,
Giving the electric field that applies the amplitude that does not reach the threshold value that causes discharge between the described electrode, regulate this frequency simultaneously, is the frequency of peak value with electric current, as described the 1st resonance frequency.
6, plasma processing method according to claim 1 is characterized in that,
Under the state of butt, regulating frequency of supply making described pair of electrodes hold solid dielectric each other under the arm, is the frequency of peak value with electric current, as described the 2nd resonance frequency.
7, plasma processing method according to claim 1 is characterized in that,
Described plasma treatment appts constitutes by transformer the back of boosting from power source voltage is powered to described telegraph circuit, constitutes described inductor by the leakage inductance of described transformer.
8, plasma processing method according to claim 7 is characterized in that,
By in inductor that constitutes by described leakage inductance and the capacitor that constitutes by described pair of electrodes, add inductor in kind or capacitor, constitute described telegraph circuit, thus, the 1st, the 2nd resonance frequency is regulated.
9, a kind of ion processing device carries out carrying out plasma treatment after the plasma to handling gas by the power supply from power supply, possesses:
Telegraph circuit, it comprises pair of electrodes and inductor, and by described power supply power supply, this pair of electrodes forms in the space between mutual opposed and imports the space of handling gas, and the opposed faces at least one side is provided with solid dielectric simultaneously; With
Frequency setting portion, it will be set in the resonance frequency of space when absence of discharge between the described electrode from the frequency of supply of described power supply to described telegraph circuit, and between the resonance frequency when regarding the space between the described electrode as conductor.
10, a kind of plasma processing method by giving the lc circuit that comprises pair of electrodes and inductor power supply, applies electric field and causes discharge for the space under the described electrode roughly normal pressure each other, and carry out plasma treatment, it is characterized in that, carries out following operation:
The operation that described electrode roughly normal pressure space is each other inferred in the natural mode shape of the described lc circuit in when discharge in advance;
Set operation, it sets frequency of supply to described lc circuit according to the mode that departs from described deduction natural mode shape; With
The plasma treatment operation, it carries out plasma treatment by the frequency power supply to set.
11, plasma processing method according to claim 10 is characterized in that,
In the described deduction operation, after described lc circuit is temporarily powered, cut-out by this power supply makes described lc circuit produce damped oscillation, and make the voltage that applies between the electrode at initial stage of this damped oscillation apply voltage about equally with setting in the plasma treatment operation, measure the frequency at the initial stage of this damped oscillation, with this measured value as described deduction natural mode shape.
12, plasma processing method according to claim 10 is characterized in that,
In the described deduction operation, the limit makes to the setting that applies in voltage and the plasma treatment operation between the described electrode and applies voltage about equally, the scan edge frequency of supply is obtained in input and output than being the frequency of great point, with this frequency as described deduction natural mode shape.
13, plasma processing method according to claim 10 is characterized in that,
In described setting operation, set frequency of supply according to producing the mode that the zone of change departs from than moment from the input and output of the periphery of described deduction natural mode shape.
14, plasma processing method according to claim 10 is characterized in that,
In described setting operation, set frequency of supply according to the mode that departs from than the zone that produces change in time from input and output at the periphery of described deduction natural mode shape.
15, plasma processing method according to claim 10 is characterized in that,
In described setting operation, frequency of supply is set in, input and output are than in the zone of stablizing in time and increasing and decreasing according to frequency of supply.
16, plasma processing method according to claim 10 is characterized in that,
In described setting operation, frequency of supply is set in, input and output than in the stable zone in time, with the zone that changes in time between the border on.
17, plasma processing method according to claim 10 is characterized in that,
In described setting operation, set frequency of supply according to roughly ± 25% above mode that departs from described deduction natural mode shape.
18, plasma processing method according to claim 10 is characterized in that,
In described setting operation, set frequency of supply according to departing from roughly ± 50% above mode of described deduction natural mode shape.
19, plasma processing method according to claim 10 is characterized in that,
In described setting operation, frequency of supply is set at the roughly scholar 50% of described deduction natural mode shape.
20, plasma processing method according to claim 10 is characterized in that,
Give the power supply of described lc circuit, undertaken by by transformer the output voltage of converter being boosted, described transformer constitutes the inductor composition of described lc circuit.
21, plasma processing method according to claim 10 is characterized in that,
Give the power supply of described lc circuit, by DC converting being become to exchange, and then boost and carry out by transformer by converter,
With the voltage Vpp between the peak value between the described electrode, with the input and output of described DC input voitage V than (Vpp/V), the parameter when carrying out described deduction operation or setting operation.
22, a kind of plasma processing method by giving the power supply of the lc circuit comprise pair of electrodes and inductor, causes discharge after the space under the described electrode roughly normal pressure is each other applied electric field, and carries out plasma treatment, it is characterized in that,
Carry out following operation:
Front travel, its make between the described electrode apply voltage and setting when handling applies after voltage equates, the scanning frequency of supply is obtained frequency of supply and the input and output relation between comparing in advance;
Set operation, it will be set in to the frequency of supply of described lc circuit, and described input and output are than in the relative scope of its maximum below given percentage; With
The plasma treatment operation, it is by powering with the frequency that sets, thereby carries out plasma treatment.
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| JP290623/2003 | 2003-08-08 | ||
| JP2003290623A JP2005063760A (en) | 2003-08-08 | 2003-08-08 | Plasma treatment method and treatment device |
| JP080168/2004 | 2004-03-19 |
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|---|---|---|---|---|
| CN102254777A (en) * | 2010-03-24 | 2011-11-23 | 东京毅力科创株式会社 | Substrate processing apparatus |
| CN102668357A (en) * | 2009-11-24 | 2012-09-12 | 泽藤电机株式会社 | Device for applying high voltage using pulse voltage, and method of applying high voltage |
| CN106255305A (en) * | 2015-06-05 | 2016-12-21 | 松下知识产权经营株式会社 | Plasma generating equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090255630A1 (en) * | 2005-04-28 | 2009-10-15 | Hitachi Kokusai Electric Inc. | Substrate processing apparatus and electrode member |
| KR101016573B1 (en) | 2008-08-05 | 2011-02-22 | 한국표준과학연구원 | Plasma generation apparatus |
| JP5787712B2 (en) * | 2011-10-20 | 2015-09-30 | 株式会社日立製作所 | Plasma processing equipment |
| DE202013005125U1 (en) * | 2013-06-04 | 2014-09-05 | Hugo Vogelsang Maschinenbau Gmbh | Device for electrical disintegration of cell aggregates |
| WO2015049781A1 (en) * | 2013-10-04 | 2015-04-09 | 東芝三菱電機産業システム株式会社 | Power-supply device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5874704A (en) * | 1995-06-30 | 1999-02-23 | Lam Research Corporation | Low inductance large area coil for an inductively coupled plasma source |
| US6170428B1 (en) * | 1996-07-15 | 2001-01-09 | Applied Materials, Inc. | Symmetric tunable inductively coupled HDP-CVD reactor |
| JP3122618B2 (en) * | 1996-08-23 | 2001-01-09 | 東京エレクトロン株式会社 | Plasma processing equipment |
| JP3840821B2 (en) * | 1998-11-30 | 2006-11-01 | 株式会社日立製作所 | Plasma processing equipment |
| JP3719352B2 (en) * | 1999-07-23 | 2005-11-24 | 三菱電機株式会社 | Power supply device for plasma generation and method for manufacturing the same |
| JP4178775B2 (en) * | 2001-08-31 | 2008-11-12 | 株式会社日立国際電気 | Plasma reactor |
| DE10154229B4 (en) * | 2001-11-07 | 2004-08-05 | Applied Films Gmbh & Co. Kg | Device for the regulation of a plasma impedance |
| JP3977114B2 (en) * | 2002-03-25 | 2007-09-19 | 株式会社ルネサステクノロジ | Plasma processing equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102668357A (en) * | 2009-11-24 | 2012-09-12 | 泽藤电机株式会社 | Device for applying high voltage using pulse voltage, and method of applying high voltage |
| CN102668357B (en) * | 2009-11-24 | 2015-03-11 | 泽藤电机株式会社 | Device for applying high voltage using pulse voltage, and method of applying high voltage |
| CN102254777A (en) * | 2010-03-24 | 2011-11-23 | 东京毅力科创株式会社 | Substrate processing apparatus |
| CN105742150A (en) * | 2010-03-24 | 2016-07-06 | 东京毅力科创株式会社 | Substrate Processing Apparatus |
| CN106255305A (en) * | 2015-06-05 | 2016-12-21 | 松下知识产权经营株式会社 | Plasma generating equipment |
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| CN100425105C (en) | 2008-10-08 |
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