CN101435074B - Substrate processing apparatus - Google Patents
Substrate processing apparatus Download PDFInfo
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- CN101435074B CN101435074B CN2008101795814A CN200810179581A CN101435074B CN 101435074 B CN101435074 B CN 101435074B CN 2008101795814 A CN2008101795814 A CN 2008101795814A CN 200810179581 A CN200810179581 A CN 200810179581A CN 101435074 B CN101435074 B CN 101435074B
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Abstract
The invention relates to a substrate processing apparatus, comprising a reaction chamber which comprises a processing chamber and an electrode chamber; the electrode chamber is separated from the processing chamber; the electrode chamber is contained with a pair of electrodes and a plurality of laminated substrates in the processing chamber; and a gas-supplying element providing the processing gas to the electrode chamber; the gas-supplying element comprises a plurality of gas-supplying openings; and the processing gas introduced from the gas introducing portion is supplied from the gas-supply openings to the reaction chamber.
Description
The application is that application number is 200510118668.7, denomination of invention is divided an application for the patented claim of " substrate board treatment ", is that application number is 03109343.4, the applying date is on April 4th, 2003, denomination of invention divides an application for the patented claim of " substrate board treatment and reaction vessel " again.
Technical field
The present invention relates to substrate board treatment and reaction vessel; Especially the substrate that uses in the fabrication of semiconductor device (substrate) treatment unit; Relevant with the substrate board treatment and the reaction vessel of treatment substrate in reaction chamber, more close with the improvement of the gas importing portion that gas is provided to substrate.
Background technology
With reference to Figure 14, be example below, briefly introduce the existing usefulness technology when adopting CVD (chemical vapour deposition) method or ALD (monoatomic layer deposition) method treatment substrate with the vertical type substrate board treatment.
Figure 14 be with the technological relevant vertical type substrate board treatment of existing usefulness in the reaction tubes of reaction chamber in the model utility sectional view.
A plurality of gas are set on 101 chew hole 103 (shown in Figure 14 5) through chewing at gas, the gas that is used in processing is got into by gas input port 105, chews in 101 along gas and advances, and chews hole 103 from gas and offers each wafer 107.
Offer after the art breading of gas to the desirable rete of each wafer 107 enforcement formation of each wafer 107, discharge outside the reaction tubess 106 by venting port 118.
Yet; Chew each gas on 101 to chew the port area in hole 103 whole when identical when being arranged on gas, by each gas chew gas flow that hole 103 offers each wafer 107 and flow velocity exist by near the upper reaches one side of gas input port 105 to away from the problem that reduces gradually of downstream one side.
That is to say; As shown in Figure 14; Among the device of a plurality of wafers 107 of unified art breading, from the viewpoint of gas being provided for every wafers, to the eye gas is chewed 101 and uniform gas is provided for every wafers 101; Difference has all taken place in gas flow and flow velocity in fact, identical condition is provided for all wafers 107.
For example when chewing hole 103 being arranged on 5 gas that gas chews on 101; By the upper reaches of chewing 101 input aperture 105 near gas; Towards away from downstream; Be set at respectively the 1st gas chew hole, the 2nd gas chew the hole ... the 5th gas is chewed the hole, the gas flow of chewing each gas hole 103 and providing be set at q1, q2 ... during q5, q1 has appearred>q2 q3 q4 the situation of q5.
In addition, it is the fastest that the flow velocity of gas has also occurred chewing the gas that hole 103 provides by the 1st gas, and down the 2nd gas chew hole, the 3rd gas chew the hole ... progressively slack-off.
The flow and the flow velocity that consequently offer the gas of each wafer 107 have all occurred inhomogeneous.
So, among the art breading of the wafer about the gas amount of providing extremely, the film that on each wafer 107 that carries, forms will inevitably occur inhomogeneous.
Return Figure 14, investigate the uneven reason of the amount of providing of this gas.
Provide the gas of gaseous phase to chew in 101 being in to wafer 107, the gas flow of input aperture 105 and the 1st gas being chewed 103 in hole is set at q00, and the pressure of gas is set at p0.The gas flow of then the 1st and the 2nd gas being chewed 103 in hole is set at q01, gaseous tension is set at p1.Identical therewith below, the gas flow that n-1 and n gas are chewed 103 in hole is set at q0 (n-1), and gaseous tension is set at p (n-1).
In addition, the gas flow of n gas being chewed hole 103 ejection is set at qn.
At this moment, by be arranged on from gas chew 101 identical a plurality of gas of the port area of swimming over to whole downstream chew the gas flow qn of ejection the hole 103 (n=1,2 ...) chew the hole to the gas in downstream and reduce gradually as chewing the hole from the gas at the upper reaches shown in the formula 1.
q1>q2>...>qn-1>qn (1)
This be because gas chew 101 in by on swim over to downstream flow gas be to have reduced when chewing hole 103 at its gas flow q0 (n-1) to flow to next gas chew the gas flow qn that hole 103 sprays from this gas after and chew the hole through gas; Chew gas flow q0n behind the hole 103 then suc as formula shown in 2 so flow through this gas, gradually reduce along with being from upstream to downstream direction.
q0n＝q0(n-1)-qn (2)
The gas density that this moment, gas was chewed the flowing gas in 101 is from upstream to downstream, reduces gradually by gas and chews the gas flow part that sprays in the hole.Because density and the gaseous tension of gas are closely related,, are from upstream to downstream and descend gradually so chew gaseous tension pn that hole 103 corresponding gas chew 101 interior positions also suc as formula shown in (3) with gas.
P1>p2>...>pn-1>pn (3)
Therefore, chew the gas flow qn of hole 103 ejection and unequal from each gas.In addition, be set at S, then chew the gas flow rate V that sprays the hole and can use shown in the formula (4) from gas as if the port area of gas being chewed hole 103.Owing to chew from each gas and to eject the hole
V＝gn/S (4)
Gas flow qn and unequal is so if the port area in nozzle hole is identical, it is also different then to chew the flow velocity of the gas that sprays the hole 103 from each gas.Therefore owing to chew among 101 at above-mentioned used gas, gas flow and the gas flow rate of chewing the gas that ejects in hole 103 from each gas are all different, thereby uniform gas are provided can't for each wafer that carries.
For the problems referred to above, two kinds of pioneering terms of settlement are arranged.
The 1st kind of terms of settlement is to be from upstream to downstream progressively to enlarge the port area that gas is chewed hole 103, increases the gas flow that reduce gradually in downstream with the way of enlarged openings area.Even if yet can make gas flow equate that shown in formula (4), along with the expansion of port area, flow velocity can dissimilate through the enlarged openings area.Therefore respectively chew the gas that sprays the hole 103 and still can't eliminate the inhomogeneous of gas flow rate from gas.
The 2nd kind of terms of settlement is gas to be chewed self manufacture the large vol gas that holds a large amount of gases that can ignore spray volume and chew; The gas flow of chewing the hole 103 ejection from each gas is equated; Even if chew in the hole 103 by gas and eject gas, chew the gaseous tensions that the gas of hole corresponding position chews in 101 with each gas and also do not change so that realize being from upstream to downstream.Yet, do not receive gas spray volume effect and unrealistic and be increased to the gaseous tensions that gas chews in 101 to the capacity that gas is chewed self because the volumetrical that will be held in the reaction chamber that gas chews limits.
And the problems referred to above are not limited to wafer but adaptable across all substrates.
Summary of the invention
For this reason, the object of the present invention is to provide a kind of from the diverse visual angle of above-mentioned structure, through gas evenly is provided, can realize the inhomogeneity substrate board treatment of the processing between substrate.
According to the 1st kind of substrate board treatment that mode provided of the present invention, it is characterized in that: this substrate board treatment comprises: reaction chamber, gas importing portion and the surge chamber of accommodating the substrate of multi-layer configuration; Above-mentioned gas importing portion is provided with along the multi-layer configuration direction of aforesaid substrate, and the gas that will be used for treatment substrate is imported above-mentioned surge chamber; Above-mentioned surge chamber has a plurality of air feed ports that are provided with along the multi-layer configuration direction of aforesaid substrate, will by above-mentioned a plurality of air feed ports above-mentioned reaction chamber be provided from the above-mentioned gas that is used for treatment substrate of above-mentioned gas importing portion input.
Owing to have this formation, the substrate board treatment that the present invention relates to can make the uneven gas of flow velocity that is provided by above-mentioned gas importing portion in above-mentioned surge chamber, become evenly, thereby can uniform gas be provided to substrate.
The port area that is arranged on a plurality of air feed ports in the above-mentioned surge chamber preferably equates.
Through the air feed port that setting has same area, can make the gas that offers substrate more even.
Be preferably in and be provided for producing isoionic electrode in the above-mentioned surge chamber.
Through being employed in the structure that produces isoionic electrode is set in the surge chamber, can near the position of substrate and with uniform pressure state, leans on plasma to generate spike, thereby can more spike evenly be provided to substrate.
According to the 2nd kind of substrate board treatment that embodiment provided of the present invention, base is characterised in that: this substrate board treatment comprises: accommodate a plurality of gas importing portion that reaction chamber, a plurality of surge chamber of the substrate of multi-layer configuration, the gas that will be used for treatment substrate are imported above-mentioned a plurality of surge chambers respectively; Above-mentioned a plurality of surge chamber has a plurality of air feed ports that are provided with along the multi-layer configuration direction of aforesaid substrate, will offer above-mentioned reaction chamber respectively by above-mentioned a plurality of air feed ports from the above-mentioned gas that is used for treatment substrate that above-mentioned a plurality of gas input ports are imported respectively.
According to the 3rd kind of reaction vessel that embodiment provided of the present invention, it is characterized in that: this reaction vessel comprises: accommodate a plurality of gas importing portion that reaction chamber, a plurality of surge chamber of the substrate of multi-layer configuration, the gas that will be used for treatment substrate are imported above-mentioned a plurality of surge chambers respectively; Above-mentioned a plurality of surge chamber has a plurality of air feed ports that are provided with along the multi-layer configuration direction of aforesaid substrate respectively, will offer above-mentioned reaction chamber respectively by above-mentioned a plurality of air feed ports from the above-mentioned gas that is used for treatment substrate that above-mentioned a plurality of gas lead-in portions are not imported.
According to the 4th kind of reaction vessel that embodiment provided of the present invention, it is characterized in that: this reaction vessel comprises: reaction chamber, gas importing portion, the surge chamber of accommodating the substrate of multi-layer configuration; Above-mentioned surge chamber has a plurality of air feed ports that are provided with along the multi-layer configuration direction of aforesaid substrate, will offer above-mentioned reaction chamber by above-mentioned a plurality of air feed ports from the above-mentioned gas that is used for treatment substrate of above-mentioned gas importing portion input.
Above-mentioned and all the other purposes of the present invention, characteristic and advantage probably can more be understood through accompanying drawing and following detailed explanation.
Description of drawings
Fig. 1 is the inner model sectional view of reaction tubes of the related substrate board treatment of the 1st embodiment of the present invention.
Fig. 2 A is the reaction tubes model sectional view of the related substrate board treatment of the 1st embodiment of the present invention.
Fig. 2 B is the longitudinal diagram along the aa ' line of Fig. 2 A.
Fig. 3 A is that the related gas of the 1st embodiment of the present invention is chewed oblique drawing.
Fig. 3 B is the oblique drawing of the related surge chamber of the 1st embodiment of the present invention.
Fig. 4 is the concise and to the point pie graph of the related vertical type substrate board treatment of embodiment of the present invention.
Fig. 5 A illustrates the outward appearance of the reaction tubes of the related substrate board treatment of the 2nd embodiment of the present invention; Fig. 5 B illustrates the concise and to the point longitudinal section of reaction tubes of the related substrate board treatment of the 2nd embodiment of the present invention, and Fig. 5 C illustrates the concise and to the point longitudinal section after the part cutting of reaction tubes of the related substrate board treatment of the 2nd embodiment of the present invention.
Fig. 6 is the transverse section along the A-A line of Fig. 5 A.
Fig. 7 is the transverse section of the reaction tubes of the related substrate board treatment of the 3rd embodiment of the present invention.
Fig. 8 is the transverse section of the reaction tubes of the related substrate board treatment of the 4th embodiment of the present invention.
Fig. 9 is the transverse section of the reaction tubes of the related substrate board treatment of the 5th embodiment of the present invention.
Figure 10 is the partial cross section of the reaction tubes of the related substrate board treatment of the 6th embodiment of the present invention.
Figure 11 is the partial cross section of the reaction tubes of the related substrate board treatment of the 7th embodiment of the present invention.
Figure 12 is the partial cross section of the reaction tubes of the related substrate board treatment of the 8th embodiment of the present invention.
Figure 13 is the transverse section of the reaction tubes of the related substrate board treatment of the 9th embodiment of the present invention.
Figure 14 is the related inner model section of processing substrate reaction tubes of existing usefulness technology.
Embodiment
Two kinds of substrate process processing mode-CVD methods that at first adopt in the embodiment more of the present invention of limit and ALD method, limit briefly introduce the film forming of the two and handle.
CVD method (chemical vapour deposition) is a kind of under certain filming condition (temperature, time etc.); The unstripped gas mixing that will be used for film forming a kind (or more than a kind) offers substrate afterwards; Adopt gas-phase reaction and surface reaction or only make it to be deposited on the substrate with the method for surface reaction, film forming method afterwards reacts.
ALD method (monoatomic layer deposition) is a kind of under certain filming condition (temperature, time etc.); The each a kind of substrate that alternately offers of unstripped gas that will be used for film forming two kinds (or two or more); Make it to utilize the film forming method of surface reaction by 1 atomic shell unit's deposition.
That is to say, when the chemical reaction that utilizes is the ALD under the film forming situation of SiN (silicon nitride), use DCS (dichlorosilane) and NH
3(ammonia) can form high-quality film under 300～600 ℃ low temperature.Corresponding with it, when adopting the CVD method, it is high that film-forming temperature is wanted relatively, usually all at 600～800 ℃.In addition,, only supply a kind of gas when adopting the ALD method from the air feed angle at every turn, alternate supplies multiple gases (not supply simultaneously), and corresponding with it CVD rule is to supply multiple gases simultaneously.And about the control of thicknesses of layers, the ALD method is to control with the supply cycle of reactant gas.(it is
/cycle for example if be set as film speed; When then needing the thickness of formation
, but 20 cycles of re-treatment.Corresponding with it CVD rule is different therewith, realizes through the period.
With reference to Fig. 1～Figure 13 embodiment of the present invention is described at this.
Common is partly used labeled among Fig. 1～Figure 13.
At first briefly introduce the basic comprising of the related vertical type substrate board treatment of various embodiment of the present invention with Fig. 4.
Fig. 4 illustrates the outward appearance of vertical type substrate board treatment.Can know by figure, this device with a plurality of processing with the crystal chip bearing of substrate-diameter 200mm in the reaction tubes that reaction chamber-quartz made, employing CVD method or ALD method art breading film forming wherein.
The supply department 61 that the vertical type substrate board treatment has main body 60 and electric power etc. is provided to main body.
In main body 60 inside, be provided with vertical type reaction chamber-reaction tubes 6 that the wafer implementing process is handled, and the well heater 16 that suitably heats this reaction tubes 6.And below reaction tubes 6, be provided with the boat 8 that makes wafer turnover reaction tubes 6 and make the up and down boat elevator 36 of this boat 8.
In addition, when needs generate plasma in reaction tubes 6, electrode 52 can be set in reaction tubes 6, apply RF power for this electrode 52 by high frequency electric source 51 through RF matching unit 53.
In addition, be provided with also in the inside of main body 60 that the storage rack 34 of the wafer storage box that above-mentioned boat 8 provides wafer is given in interim keeping and the wafer before handling is provided to boat 8 from this storage rack 34, take out the wafer transfer machine 38 of the wafer after the processing.
And award between the I/O Stage microscope 33 of wafer case 32 at storage rack 34 and extraneous the receipts, be responsible for carrying wafer case 32 by wafer case hopper loader 35.
I/O Stage microscope 33 is arranged on the device front, awards the wafer case 32 of accommodating wafer with outside receipts of device.
Briefly introduce the action of above-mentioned vertical type substrate board treatment at this.
The wafer case of having accommodated wafer 32 is installed on the I/O Stage microscope 33.
Be contained in the wafer case 32 on the I/O Stage microscope 33, transport to successively on the storage rack 34 by wafer case hopper loader 35.
Accommodate 25 wafers among each wafer case 32.
The action one of filling wafer finishes on the boat 8, and boat 8 promptly leans on boat elevator 36 to rise, insertion reaction pipe 6, and after this resistance to air loss remains within the reaction tubes 6.
Gas in the reaction tubes 6 is discharged with pump by not shown venting port, promptly makes boat 8 execute commentaries on classics through not shown swivel arrangement in case reach the pressure of regulation, and offers reaction tubes to the gas that is used for the film forming processing of rated flow.The gas that is used to handle that is provided leans on not shown regulator keeping rated pressure.At this moment, reaction tubes 6 inner wafers lean on well heater 16 keeping temperature rating.
On wafer, carrying out the content of the technical process of film forming processing like this will introduce below.
In addition; At this moment adopt plasma CVD method or ALD method to carry out under the situation of film forming processing; About applying RF power for electrode 52 through RF matching set 53 by high frequency electric source 51; Generate plasma in above-mentioned being used among the film forming gas, this content of operation that is used for film forming gas activation of enforcement of going forward side by side also will be introduced at the back literary composition.
Become membrane treatment process one to finish, 8 of wafer boat lean on boat elevator 36 from reaction tubes, to descend, and through wafer transfer machine 38, storage rack 34, wafer case hopper loader 35, are sent on the I/O Stage microscope 33, and then deliver to outside this device.
Introduce the embodiment that adopts above-mentioned vertical type substrate board treatment below.
(the 1st embodiment)
This mode is in becoming membrane treatment process, to use the embodiment of CVD method.
Fig. 2 A is the model transverse section of the reaction tubes in the related vertical type substrate board treatment of this embodiment, and Fig. 2 B is the longitudinal section along Fig. 2 Aa-a '.
Among Fig. 2 A, be provided with well heater 16 in the periphery of vertical type reaction chamber-reaction tubes 6, portion is as a plurality of substrates that are processed object within it, and multilayer is being carried wafer 7.
In addition, in the inwall and the circular arc space between the wafer 7 of reaction tubes 6, in the bottom of reaction tubes 6 to the inwall on top; Loading direction along wafer; Be provided with surge chamber 17, on the adjacent chamber wall of this surge chamber 17 and wafer 7, be provided with the buffer chamber hole 3 that uses as air vent.The opening of this buffer chamber hole 3 faces the center of reaction tubes 6.
And in this surge chamber 17 with the rightabout the other end of an end of buffer chamber hole 3 is set, be still and disposed the gas that is arranged on gas importing portion to top along the loading direction of wafer 7 from the bottom of reaction tubes 6 and chew 2.And chew at this gas and to be provided with a plurality of gas on 2 and to chew hole 4.
In addition, shown in Fig. 2 B, the periphery of reaction tubes 6 is covered by well heater 16.And reaction tubes 6 is supported that by fire door ring flange 25 fire door of fire door ring flange 25 is by furnace access cap 27 sealings.
Central part in the reaction tubes 6 is provided with the boat 8 that is loading a plurality of wafers 7 with the layering of same interval, and this boat 8 is set at and can debouches reaction tubes 6 through above-mentioned boat elevator.In addition, in order to improve the homogeneity of processing, below boat 8, be provided with the swivel arrangement 15 that is used for rotating boat 8.
In boat 8 gets into reaction tubess 6, wafer is carried out during film forming handles, each wafer 7 that layering is loaded keeps equidistant state with surge chamber 17.
Inwall along reaction tubes 6 is provided with surge chamber 17, and reaction tubes 6 one sides in surge chamber 17 have disposed gas from bottom to top and chewed 2, then form gas input port 5 in its underpart.Gas chew 2 with surge chamber 17 on be provided with above-mentioned gas and chew hole and buffer chamber hole, illustrate by Fig. 3 A, Fig. 3 B about the open state in this hole.
Fig. 3 A is the oblique drawing that the gas shown in Fig. 2 A～Fig. 2 C is chewed, and Fig. 3 B is the oblique drawing of the surge chamber shown in Fig. 2 A～Fig. 2 C too.
Gas shown in Fig. 3 A is chewed (gas jet) the 2nd, and section is circular tubing; Chew 2 topmost is provided with to the surge chamber bottom by the gas that the downstream rectilinearity arranges of swimming over to of gas and chews hole 4 from this gas in its side; And its port area is swum end (being the below among Fig. 3 A) from it and is become greatly gradually to downstream end (being the top among Fig. 3 A) from the angle of above-mentioned gas input aperture.
Return Fig. 2 B below.
Side in reaction tubes 6 bottoms is provided with the venting port 18 that is connected with not shown off-gas pump.
, explain with reference to Fig. 2 A, Fig. 2 B at this with regard to adopting CVD methods film-forming process of depositional coating on the wafer 7 in the reaction tubes 6.
The processing gas that is formed into the pleurodiaphragmatic in terspace material offers gas from gas input port 5 and chews 2.Chew on 2 at gas, be provided with a plurality of above-mentioned gas and chew hole 4, gas is sprayed into surge chamber 17.Yet,,, be difficult to make that to chew the flow of the gas of ejection the hole 4 from a plurality of gas identical with flow velocity if only control the port area that gas is chewed hole 4 as as being introduced in forerunner's property terms of settlement.
Therefore among the present invention, the port area through gas being chewed hole 4 from swim over to downstream and progressively strengthen, though make the gas of chewing ejection the hole 4 from each gas that the difference of flow velocity aspect arranged, its flow is identical substantially.And be not this each gas to be chewed the gas that sprays in the hole 4 directly spray into reaction tubes 6, but at first be sprayed onto among the surge chamber 17, make the difference equalization of above-mentioned gas flow velocity aspect.
That is to say that among surge chamber 17, the gas of chewing hole 4 ejection by each gas relaxes its each gas particles surge chamber 17 in speed is sprayed onto in the reaction tubes 6 by buffer chamber hole 3 afterwards again.Therebetween, owing to chew the gaseous interchange kinergety each other of hole 4 ejections from each gas, thereby when each buffer chamber hole 3 sprays, can make it to become gas with uniform flux and flow velocity.
About the homogeneity of the air demand in above-mentioned surge chamber 17, further explain with reference to Fig. 1 below.
Fig. 1 is that the inner gas of reaction tubes of expression vertical type substrate board treatment involved in the present invention is chewed, the model sectional view of surge chamber, wafer mutual relationship.
Among Fig. 1, be provided with surge chamber 17 in the reaction tubes 6, in surge chamber 17, dispose gas and chewed 2, also be provided with the venting port 18 of discharging gas in the reaction tubes 6.
Adjacent with surge chamber 17 in reaction tubes 6, also be provided with the boat 8 of bearing wafer 7 (among Fig. 1 for carry 5).
Gas chew 2 with surge chamber 17 on, be provided with gas and chew hole 4 and buffer chamber hole 3, (Fig. 1 is for respectively being provided with 5), gas is chewed the port area in hole 4, from the angle of gas input port, is from upstream to downstream and becomes big gradually.
Adopt and to constitute; When the upstream extremity near input aperture 5 is set at the 1st hole, the 2nd hole respectively to the downstream end away from the input aperture on 2 chewing from gas ... the 5th hole; When being set at Q1, Q2...Q5 to the gas flow of chewing hole 4 from each gas and providing, can make Q1=Q2=...Q5.
Yet in forerunner's property terms of settlement, having introduced, aspect the flow velocity of gas, the gas flow rate of chewing ejection the hole 4 from the gas in the 1st hole is maximum, diminishes gradually in thereafter the 2nd hole, the 3rd hole.
Flow is identical but the air-flow of Q1～Q5 that flow velocity is different at first is transfused to surge chamber 17.Therebetween, the energy exchange that the air communication of Q1～Q5 is crossed each other becomes evenly the difference of flow velocity aspect, thereby the pressure in the surge chamber 17 become basic identical.
Its result; When being R1, R2...R5 to the flow set of the air-flow of ejection from each buffer chamber hole 3; Even if the port area of each buffer chamber hole 3 is identical, so but because the pressure in the surge chamber 17 is even in R1=R2=...R5, it is identical that its flow velocity also becomes.
It is identical at interval preferably to be set at respectively adjacent with it wafer 7 to each aperture position of buffer chamber hole 3 in addition, through setting the compartment that gas is offered 7 of each wafers of loading, flow and flow velocity all the gas of equalization efficiently offer wafer 7.
Through flow and flow velocity all the gas of equalization efficiently offer wafer 7, except the one-tenth membrane stage that can make 7 of each wafers become more even, also can increase substantially the art breading speed of wafer 7.
Among above-mentioned introduction be that example has recorded and narrated that gas is chewed, the formation of surge chamber, yet this structure is equally applicable to the ALD method with CVD.
(the 2nd embodiment)
This mode is in becoming membrane treatment process, to have used the embodiment of ALD method.
Just adopt the film forming embodiment of ALD method to specify below.
On wafer 7, during film forming, also can use the substrate board treatment of above-mentioned vertical type when adopting the ALD method.But adopting under the situation of ALD, when requiring to adopt plasma etc. to make to handle gas activation, need in this process, increase the device and the operation of necessity.
Explain with the film forming situation of ALD method with Fig. 5 A, 5B, 5C and Fig. 6 below.
Fig. 5 A, 5B, 5C use when never ipsilateral is illustrated in employing ALD method film forming, the outward appearance of the reaction chamber-reaction tubes in the vertical type substrate board treatment involved in the present invention and inner figure, and Fig. 6 then is its A-A transverse section.
Among Fig. 5 A, 5B, 5C, Fig. 5 A illustrates the outward appearance of reaction chamber, and Fig. 5 B, Fig. 5 C illustrate the longitudinal section of reaction chamber, and junction surface, the boat swivel arrangement of well heater, wafer, boat, reaction tubes and fire door ring flange then omit.
Among Fig. 6, the periphery of reaction tubes is provided with well heater 16, side within it, and as the substrate of a plurality of process object, multilayer is being carried wafer 7.In the inwall of reaction tubes 6 and the circular arc space between the wafer 7, lean on reaction tube one side, be provided with surge chamber 17, on the wall of an adjacent side, be provided with buffer chamber hole 3 with wafer along the loading direction of wafer 7.
In addition, be provided with venting port 18 in the bottom of reaction tubes 6.
Among the reaction tubes of in Fig. 2 A, explaining; Gas chew be configured in surge chamber in the rightabout the other end of an end of buffer chamber hole is set, and among the related reaction tubes of this embodiment, do not have gas to chew; Replace its function but disposed air supply chamber 43, be provided with gas input port 5 in its underpart.
And; On the space bar of air supply chamber 43 and surge chamber 17, be provided with to have and chew set gas with above-mentioned gas and chew the identical air supply chamber hole 47 of pore structure, and the aperture position that will be arranged on each buffer chamber hole 3 on the surge chamber 17 be separately positioned on the identical at interval position of adjacent with it wafer 7 on.
Its result is described in the 1st embodiment, in case import each wafer that gas can offer gas carrying equably from gas importing portion.
In addition, among this embodiment, the electrode 52 that disposes from top to bottom in the surge chamber 17, by 50 protections of electrode protection pipe, this electrode 52 is connected with high frequency electric source 51 through RF matching unit 53.
Its result can make electrode 52 in surge chamber 17, produce plasma 14.
In this embodiment, calculate from the aperture position of buffer chamber hole 3, about 120 ° of reaction tubes 6 inwalls the position on set up reactant gases surge chamber 42.This reactant gases surge chamber 42 is to use ALD method film forming, a kind of gas is provided at every turn, when alternately multiple gases being provided, being used for sharing gas jointly with surge chamber 17 and supplying with kind for wafer 7.
This reactant gases surge chamber 42 is also the same with surge chamber 17, with the wafer position adjacent on the same reactant gases buffer chamber hole 48 that is interval with, be provided with reactant gases input aperture 45 in its underpart.Yet be with surge chamber 17 differences: it does not have air supply chamber 43 and electrode 52.In addition, reactant gases buffer chamber hole 48 also has its port area and is from upstream to downstream and becomes big structure gradually.
Venting port 18 is located at the bottom of reaction tubes 6, but states ALD method film forming in the use, to wafer a kind of gas is provided, and when alternately multiple gases being provided, this venting port 18 forms the structure that can get rid of reaction tubes 6 internal gas.
Fig. 5 A is that outward appearance and inside (the dotted line sign) of the reaction tubes 6 can be from top view surge chamber 17 time constitutes.
In reaction tubes 6, be provided with surge chamber 17 from top to bottom, with the surge chamber 17 adjacent air supply chambers 43 that are provided with.And within surge chamber 17, disposed from top to bottom by the electrode 52 of electrode protection pipe 50 protections, be provided with gas input port 5 in the bottom of air supply chamber 43.
These electrode protection pipe 50 formation can make the electrode 52 of slim-lined construction to insert the structure in the surge chamber 17 with the isolated state of the atmosphere of surge chamber 17.At this, owing to electrode protection pipe 50 inside are and the identical atmosphere of outside gas (air), might be oxidized so insert the electrode 52 of electrode protection pipe 50 because of the heating of not shown well heater.For this reason, the inner setting of electrode protection pipe 50 is the non-active gas treatment facilities, adopts non-active gas or purifying methods such as filling nitrogen, fully suppresses oxygen concentration wherein.
On the position of inner wall surrounding certain distance from this surge chamber 17 along reaction tubes 6, be to be provided with reactant gases surge chamber 42 from top to bottom equally, be provided with reactant gases input aperture 45 in its underpart.
In addition, from the opposite direction of surge chamber 17 courts and reactant gases surge chamber 42, along being provided with venting port 18 on the lower position of reaction tube around certain distance.
Fig. 5 B is the inner case of buffer chamber hole 3 and reactant gases buffer chamber hole 48 reaction tubes 6 when being in the top view position.
In reaction tubes 6, be provided with surge chamber 17 and adjacent with it air supply chamber 43 from top to bottom, in surge chamber 17, have the buffer chamber hole 3 of same port area with uniform distances being provided with from top to bottom with on the not shown wafer position adjacent.And buffer chamber hole 3 has same port area on the wall of the chamber of the surge chamber with same thickness 17.
From this surge chamber 17 position around reaction tubes 6 inwall certain distances, be from top to bottom equally, be provided with reactant gases surge chamber 42.And, in reactant gases surge chamber 42, from top to bottom with not shown wafer position adjacent on be provided with reactant gases buffer chamber hole 48 with same interval.And the structure of the port area of reactant gases buffer chamber hole 48 is: being from upstream to downstream, then is from bottom to top to strengthen gradually among Fig. 5 A, 5B, 5C.
Fig. 5 C is the longitudinal diagram for the reaction tubes 6 that is arranged on the air supply chamber hole 47 on the air supply chamber 43 from top view.
In reaction tubes 6, be provided with air supply chamber 43 from top to bottom with on surge chamber 17 position adjacent.And on the spaced walls of surge chamber 17 and air supply chamber 43, by top to also being provided with air supply chamber hole 47 by time many bottoms with not shown wafer consecutive position.It is not produce the gas precipitation district in the surge chamber 17 in order to allow that the opening in air supply chamber hole 47 extends to surge chamber reason bottom always.
And that the port area in air supply chamber hole 47 and the gas that the gas shown in Fig. 3 A is chewed are chewed the hole is identical, has adopted the formation that downstream direction strengthens gradually of swimming over to from gas.
With reference to Fig. 5 A, 5B, 5C and Fig. 6 the situation that adopts ALD method deposited film on the interior wafer 7 of reaction tubes 6 is described below.
In this film forming example, introduce as handling gas, ammonia (NH alternately is provided
3) spike and dichlorosilane (SiH
2Cl
2) gas, adopt atomic shell to become embrane method to form the method for SiNx film (silicon nitride film).
Filling 100 wafers in reaction tubes 6, and make the reaction tubes 6 inner airtight conditions that keep.Adopt not shown pump,, and make a certain specified temperature that keep in the reaction tubes 6 in 300～600 ℃ of scopes through the temperature of regulating well heater 16 through vapor pipe 18 gas in the reaction tubes 6 of draining.
At first offer air supply chamber 43 to ammonia from gas input port 5.
For the ammonia flow that is sprayed onto from here in the surge chamber 17 is equated, therefore be designed to port area to strengthen gradually from the downstream of swimming over to of air-flow.
Therefore be sprayed onto the ammonia of surge chamber 17 from air supply chamber hole 47, fast downstream are slow though its flow velocity is the upper reaches, and its flow then is that all air supply chamber hole 47 is all the same.
In a single day this ammonia that is sprayed onto in the surge chamber 17 is transfused to here, through exchanging the difference equalization that kinetic energy makes the flow velocity aspect each other, thereby makes surge chamber 17 pressure inside equalizations.
Be transfused to surge chamber 17 at ammonia; Under the state that pressure between the 1 counter electrode protective tube equates; If the RF power that high frequency electric source 51 is come offers the stick electrode of inserting in two electrode protection pipes 50 that are arranged in the surge chamber 17 52 through RF coupling mechanism 53, will between electrode protection pipe 50, generate plasma 14.
And within surge chamber 17; Through the ammonia plasma; Generate the spike (crystal seed) of ammonia; And owing to be that generation is isoionic under the uniform situation of pressure in surge chamber 17 at this moment, because the distribution of influential isoionic electronic temp of the life of spike and plasma density is also become evenly, thereby can generate the more uniform spike of distribution.
Because the spike that generates by effects such as plasmas has its life-span; If the hypertelorism between plasma maker and the wafer 7; Wafer 7 inactivation before will offered; Thereby cause the consequence that the acting spike quantity of the reaction on the wafer 7 is significantly reduced, so isoionic generation is preferably in nearby carrying out of wafer 7.
Should constitute if adopt, owing to nearby generate the ammonia spike at surge chamber 17 these wafers 7, thereby can offer wafer 7 to the spike of a large amount of ammonias that generate expeditiously.
And the interval of two electrode protection pipes 50 preferably is set at suitable distance; 20mm preferably; So that the generation of plasma 14 is limited within the surge chamber 17, in addition, though isoionic generation can be at surge chamber 17 Anywhere; But the gas that preferably makes input buffering chamber 17 is the best through among this plasma with the mid-way that is arranged on buffer chamber hole 3 and air supply chamber hole 47.
In addition, should be adjusted into appropriate intervals to the distance between electrode protection pipe 50 and the buffer chamber hole 3 in advance, leak into outside the surge chamber 17 so that the plasma 14 that generates in the surge chamber 17 is unlikely to diffusion.
Its result is because to offer the whole of wafer 7 by buffer chamber hole 3 be that electrical characteristic are the spike of neutral ammonia, so the damage that can avoid the electric He because of wafer 7 to rise and cause.
As above-mentioned, because buffer chamber hole 3 its port areas that are arranged on the surge chamber 17 are all identical, and owing to the spike that offers the ammonia of wafer 7 can provide with uniform flow rate and even flow, thereby can carry out uniform film forming to each wafer and handle.
In addition, because buffer chamber hole 3 is arranged on the mid-way at interval of multilayer bearing wafer 7, thereby can competent processing gas be provided to each wafer 7.
And among the ALD method that alternately provides different types of processing gas to form from level to level film as thin as a wafer; Through pressure and the temperature in the suitable setting reaction tubes 6; When forming one deck by the providing of spike of this ammonia and contain the very thin films of N atom; Scope limits and will work, and thickness can further not increase.
When the surface of entire wafer 7 all formed the very thin films of nitrogen atom, the RF electric power that is applied on the electrode 52 promptly was cut off, and stopped the supply of ammonia.
Then, N is used on the limit
2Reach non-active gas purification reaction tubes 6 inside such as Ar, the limit is discharged these gases by venting port 18.Then moment of fully descending of the concentration of the spike of the ammonia in reaction tubes 6, stop to supply with above-mentioned non-active gas,, dichlorosilane gas is imported reactant gases surge chamber 42 by reactant gases input aperture 45.
Among reactant gases surge chamber 42, be provided with by swimming over to downstream on the reactant gases input aperture 45 the reactant gases buffer chamber hole 48 that port area enlarges gradually towards the center of reaction tubes 6.So, though the dichlorosilane flow velocity difference flow that offers wafer by reactant gases buffer chamber hole 48 be sprayed onto in the reaction tubes 6 identically.
Certainly; If do not use reactant gases surge chamber 42 that dichlorosilane gas is provided; But cover air supply chamber 43 identical with the equipment that provides ammonia to use and adjacent with it surge chamber 17 are set in reaction tubes 6 in addition, flow and flow velocity are all kept evenly then can be better.
Yet among this embodiment,, also might on wafer 7, form well-proportioned film if the use that provides of dichlorosilane gas equates gas flow than the easy more reactant gases surge chamber 42 of the combination of air supply chamber 43 and surge chamber 17.
In case on the surface of wafer 7, form siliceous very thin films, promptly stop to provide of dichlorosilane.Then use N
2Reach non-active gas purification reaction tubes inside such as Ar, and these gases are discharged from venting port 18, in the moment that the dichlorosilane concentration in reaction tubes fully descends, stop to supply with non-active gas.
Adopt above-mentioned a series of art breading; Can form the silicon nitride film of
approximately; Therefore for example when need under the situation of the silicon nitride film that forms
on the wafer 7, approximately needing 500 above-mentioned technologies of repetition.
And rotate with certain speed through the not shown boat that makes bearing wafer 7, even, can realize on entire wafer 7 that also film forming is handled more uniformly from a side air feed of wafer 7.Among this embodiment, its speed of rotation is if there is 1～10rpm just enough.
Therefore, under the non-rotary situation of boat, the homogeneity of the thickness of wafer 7 is about ± and 5%, and under the situation of rotation boat, its error is less than ± 1%.
(the 3rd～the 5th embodiment)
This is a different embodiment of in becoming membrane treatment process, using the ALD method.
Fig. 7 is the transverse section of the reaction tubes of the related vertical type substrate board treatment of the 3rd embodiment of the present invention.
Utilize the luminous energy of uv lamp 54 to make the reactant gases activation.
The processing gas that in the surge chamber with above structure 17, is activated is sprayed on wafer by buffer chamber hole 3, on wafer 7, forms rete with above-mentioned ALD method.
Fig. 8 is the transverse section of the reaction tubes of the related vertical type substrate board treatment of the 4th embodiment of the present invention.
Have the proper resistor value as this, can produce the electric heater 55 of spike, use the tungsten filament about 0.5mm the most suitable.
Utilize the electric power of power supply 57 that this electric heater is heated to more than 1600 ℃, utilize heat energy to activate the processing gas of contact with it.
The processing gas that in the surge chamber with above formation 17, is activated towards wafer 7 ejections, adopts above-mentioned ALD method on wafer, to form rete by buffer chamber hole 3.
Fig. 9 is the transverse section of the reaction tubes of the related vertical type substrate board treatment of the 5th embodiment of the present invention.
The gas of the processing usefulness through distance type plasma generator 56 reacts with plasma herein and is activated; This gas that is activated gets into reaction tubes 6 by gas input port 5; Offer surge chamber 17 through air supply chamber 43; And then, offer wafer, and adopt above-mentioned ALD method on wafer, to form rete as uniform gas from being arranged on the buffer chamber hole 3 on this surge chamber 17.
At this,, use the ICP coil the most suitable as distance type plasma generator 56.
Adopt and should constitute, compare with the device of Fig. 6, the quantity of the spike of wafer reduces, processing efficiency descends though offer, and under to the situation of processing efficiency no requirement (NR), still can use.
(the 6th～the 8th embodiment)
Introduce the 6 8th embodiment of the present invention with reference to Figure 10,11,12 below.Figure 10, Figure 11, Figure 12 are respectively the transverse section of the left-half of the reaction tubes 6 that uses in the processing substrate treatment unit of the 6th, the 7th, the 8th embodiment of the present invention.
Among the 6th, the 7th, the 8th embodiment that Figure 10, Figure 11, Figure 12 illustrate respectively, identical with the 1st embodiment, gas chew 102 from the bottom of reaction tubes 6 direction one on top of another along wafer 7 is configured within the surge chamber 17 up to top.Gas is chewed 102 bottom and is communicated with gas input port 5.Chew at gas and vertically to be provided with many gas on 102 and to chew hole (not shown).In addition, identical with the 1st～the 5th embodiment, though not shown, on the lower side of reaction tubes 6, be provided with the venting port that links to each other with not shown off-gas pump.
Among the 6th embodiment shown in Figure 10; Portion's chamber-separating wall 172 of surge chamber 17 is shared with the part tube wall of reaction tubes 6; Two electrode protection pipes 50 are configured in the wall 174 of this chamber wall 172 to be compared, more on the position near 173 walls of portion's chamber-separating wall 171 of the surge chamber that is provided with buffer chamber hole 3 17.Also be configured in the wall 174 of chamber wall 172 by two electrodes 52 of two electrode protection pipes 50 protection and compare, (distance between the wall 173 of the chamber wall 171 of electrode protection pipe 50 and surge chamber 17 is preferably 0～5mm on the position near the wall 173 of chamber wall 171 more.Here said 0mm is meant that electrode protection pipe 50 is close to wall configuration).Two electrodes 52 and two electrode protection pipes 50 are crossed over buffer chamber hole 3 configurations, (being that buffer chamber hole 3 is between two electrode protection pipes 50).This structure can make the plasma 14 and the distance of buffer chamber hole 3 become the shortest.
Through making the wall 173 of two electrode protection pipes 50, can limit main gas flow path near the chamber wall 171 that constitutes surge chamber 17.Through buffer chamber hole 3 being set on through the position between two electrode protection pipes 50, can make reactant gases in addition, thereby the density of spike is increased efficiently through the high zone of plasma 14 density at limited main gas flow path.
Under the situation of Figure 10, the reactant gases path in the surge chamber 17 can be divided into path D, path E, path c, path f substantially.Path D, path E form main gas flow path, and the more than half of reactant gases will be from passing through just from the big zone passage of plasma 14 density between two the two poles of the earth protective tubes.
In addition, because plasma 14 is very near apart from buffer chamber hole 3, and the retardance of unnecessary air-flow also is controlled in the inferior limit, thereby the inactivation of the spike that can generate D, path E in the path be controlled in the bottom line.In addition, even if at the last stage inactivation that gets into buffer chamber hole, also can activate once again through plasma 14.
In addition; The path c of those 50 of two electrode protection pipes of not flowing through, the air-flow of path f; Because it must be through near the plasma 14 before getting into buffer chamber hole 3; Thereby the density of its spike also can increase, and path c also the same with path D before input reaction chamber 6 inactivation seldom.
That is to say, adopt this embodiment can realize following each item.
1. can activate by enough high-density plasmas.(the active density on activationary time point)
2. can with the spike non-inactivation deliver to and be processed substrate (wafer 7).
Needn't control in order to eliminate path D and path E to go up the density variation of spike and form spike gas flow path before also is the characteristic of this embodiment.
At this because as long as be adjacent to surge chamber 17 to electrode protection pipe 50; Just can cut off path c and path f, and only remaining gas path D and E, thereby can highdensity spike effectively be provided to being processed substrate; In addition; Owing to eliminated the gap that road c, f pass through, do not had error because the reactant gases between device activates density, so better effects if.
Figure 11 illustrates the 7th embodiment; Chew the 102 gas rectilinearity that provide (path F) through plasma 14, buffer chamber hole 3 for making gas; Thereby with gas chew 102 and buffer chamber hole 3 be configured between two electrode protection pipes 50, identical with Figure 10, all be the formation that can increase spike density.
Figure 12 illustrates the 8th embodiment; One in two electrode protection pipes 50 near constituting surge chamber 17; The wall 173 of the chamber wall 171 of buffer chamber hole 3 is set; And another root electrode protection Guan Ze limits main gas flow path near the wall 174 of the shared portion's chamber-separating wall 172 of reaction tubes 6 and surge chamber 17 with this.On the main position of gas flow path I, be provided with buffer chamber hole 3 through 50 of two electrode protection pipes.
If do comparison with the embodiment of Figure 10 and Figure 11; The distance that will find plasma 14 and buffer chamber hole 3 becomes big; And produced the air-flow retardance thereupon, but pass through one in the electrode protection pipe wall 173 near the chamber wall 171 that constitutes surge chamber 17, thereby inactivation can be reduced.
As above-mentioned, through making surge chamber 7, electrode protection pipe 50, and the configuration optimizing of buffer chamber hole 3, the density of spike that can augmenting response gas.
The optimizing of the relative position through surge chamber 17, electrode protection pipe 50, buffer chamber hole 3 improves the density of the spike of reactant gases and introduces in the above; But when the uniformity of treatment between other each treatment unit of angle consideration, safety, repeatability, then preferably adopt consistent relative position.
In above-mentioned example, because electrode protection pipe 50, surge chamber 17 and buffer chamber hole 3 are independent separately, and produce assembly error, thereby can be in the discordance between generation device aspect the reactant gases sensitization concentration.
Thereby, then might suppress above-mentioned discordance if adopting chamber wall, buffer chamber hole 3, the electrode protection pipe 50 of reaction tubes 6, formation surge chamber 17 is the reaction tubes of one altogether.If material separately all adopts quartz, then should be out of question through dissolving integral body of formation.
In addition, because in above-mentioned example, used electrode protection pipe 50, thus with regard to the position of electrode protection pipe 50 in addition explanation, but under the situation of not using electrode protection pipe 50, the position of electrode 52 we can say same as described above.
If adopt the structure shown in above-mentioned the 6th～the 8th embodiment, then identical with the 1st embodiment, can be used as the CVD device and use, and also as shown in Figure 6, if outside surge chamber 17, increase a surge chamber 42 in addition, then can be used as the ALD device and use.
(the 9th embodiment)
Introduce the 9th embodiment of the present invention with reference to Figure 13 below.
This embodiment is on the device of the 6th embodiment shown in Figure 10, to increase another surge chamber 42 shown in Figure 6, uses as the ALD device.
Chew at gas and vertically to be provided with many gas on 102 and to chew hole 103.This gas is chewed wall 176 settings of hole 103 towards the chamber wall 175 of surge chamber 17.Be provided with as if gas being chewed the inboard of hole 103 courts with wall 176 rightabout surge chambers 17; 102 ammonia is provided, dichlorosilane gas is provided such alternately the chewing of the 2nd embodiment for example from surge chamber 42 from gas; Adopt the ALD method to form under the situation of silicon nitride film, can be detained at ammonia, the secondary resultant of formation reaction property and form particulate when dichlorosilane gas flows.Therefore, gas is chewed wall 176 settings of hole 103 towards the chamber wall 175 of surge chamber 17, after ammonia is provided, purify, ammonia is detained, thereby can prevents that particulate from taking place with non-active gas.
In above-mentioned the 6th～the 8th embodiment; Chew 102 lateral longitudinal at gas and chew hole (not shown) to being provided with many gas; Gas in above-mentioned the 9th embodiment is chewed 102 side and also vertically is provided with many gas and chews hole 103, is set at specified length but also can chew 102 to gas, gas is chewed 102 top and is set at opening; In the case, gas is chewed 102 height and preferably is positioned on the loading position position on the lower side than wafer 7.
Illustrate above all exemplary embodiment and in addition explanation.But the present invention is not limited to these embodiments.Therefore, scope of the present invention only receives the qualification of right claimed range.
Claims (3)
1. substrate board treatment is characterized in that comprising:
Reaction vessel comprises treatment chamber and electrode vessel, and above-mentioned electrode vessel and above-mentioned treatment chamber are separated, and above-mentioned electrode vessel accommodates pair of electrodes and a plurality of substrate of lamination of treating is contained in the above-mentioned treatment chamber; With
Air feed spare will be handled gas into above-mentioned electrode vessel will be provided, and above-mentioned air feed spare comprises a plurality of air feed ports, wherein
Above-mentioned pair of electrodes is extended along the stack direction of above-mentioned a plurality of substrates, and above-mentioned electrode is arranged on a side of above-mentioned a plurality of substrates, and high frequency electric source is provided for above-mentioned electrode,
Above-mentioned electrode vessel is configured to, and all electrodes that are used to activate a kind of gas are configured in a side of substrate,
Supply with the gas that is activated from a side direction treatment chamber of treatment chamber, thus substrate handled,
Wherein, on substrate, form film through supply gas.
2. substrate board treatment as claimed in claim 1 is characterized in that,
Spray to the relative substrate surface along continuous straight runs of processing gas of treatment chamber ejection from the air feed port of electrode vessel, and substrate is handled.
3. substrate board treatment as claimed in claim 1 is characterized in that,
Have the bottom that is connected the range upon range of zone of the interior a plurality of substrates of treatment chamber, the venting port of discharging processing gas.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002104011A JP3957549B2 (en) | 2002-04-05 | 2002-04-05 | Substrate processing equipment |
| JP104011/2002 | 2002-04-05 | ||
| JP203397/2002 | 2002-07-12 | ||
| JP2002203397A JP4281986B2 (en) | 2002-07-12 | 2002-07-12 | Substrate processing equipment |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031093434A Division CN100459028C (en) | 2002-04-05 | 2003-04-04 | Substrate board treatment device and reaction container |
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| Publication Number | Publication Date |
|---|---|
| CN101435074A CN101435074A (en) | 2009-05-20 |
| CN101435074B true CN101435074B (en) | 2012-03-07 |
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| CN 200510118668 Pending CN1789489A (en) | 2002-04-05 | 2003-04-04 | Substrate processing apparatus |
| CN2008101795814A Expired - Lifetime CN101435074B (en) | 2002-04-05 | 2003-04-04 | Substrate processing apparatus |
| CNB2005101186672A Expired - Lifetime CN100480421C (en) | 2002-04-05 | 2003-04-04 | Reaction container |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP3957549B2 (en) | 2007-08-15 |
| CN1789488A (en) | 2006-06-21 |
| CN101435074A (en) | 2009-05-20 |
| CN100480421C (en) | 2009-04-22 |
| JP2003297818A (en) | 2003-10-17 |
| CN1789489A (en) | 2006-06-21 |
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