CN1279577C - Thermally processing substrate - Google Patents
Thermally processing substrate Download PDFInfo
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- CN1279577C CN1279577C CNB018144985A CN01814498A CN1279577C CN 1279577 C CN1279577 C CN 1279577C CN B018144985 A CNB018144985 A CN B018144985A CN 01814498 A CN01814498 A CN 01814498A CN 1279577 C CN1279577 C CN 1279577C
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- matrix
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- 239000000758 substrate Substances 0.000 title claims abstract description 19
- 238000010926 purge Methods 0.000 claims abstract description 136
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000007789 gas Substances 0.000 claims description 159
- 239000011159 matrix material Substances 0.000 claims description 120
- 238000010438 heat treatment Methods 0.000 claims description 85
- 238000003860 storage Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 239000001307 helium Substances 0.000 claims description 18
- 229910052734 helium Inorganic materials 0.000 claims description 18
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 21
- 230000004044 response Effects 0.000 abstract description 7
- 238000003672 processing method Methods 0.000 abstract 1
- 239000006163 transport media Substances 0.000 abstract 1
- 239000012530 fluid Substances 0.000 description 12
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000005086 pumping Methods 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004151 rapid thermal annealing Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/10—Heating of the reaction chamber or the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
- C30B31/12—Heating of the reaction chamber
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
- H01L21/67109—Apparatus for thermal treatment mainly by convection
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
- H01L21/67115—Apparatus for thermal treatment mainly by radiation
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A thermal processing method is described in which a temperature response of a substrate may be controlled during a heat-up phase or a cool-down phase, or during both phases. This reduces the thermal budget of the substrate . In particular, by controlling the rate of heat transfer between the substrate and a thermal reservoir (e.g., a water-cooled reflector plate assembly), the temperature response of the substrate may be controlled during the thermal process. The rate of heat transfer may changed by changing the thermal conductivity between the substrate and the thermal reservoir, by changing the emissivity of a surface of the thermal reservoir, or by changing the distance between the substrate and the thermal reservoir. The thermal conductivity may be changed by changing the characteristics of a thermal transport medium (e.g., a purge gas) located between the substrate and the thermal reservoir.
Description
The cross reference of related application
The application is that submission on July 8th, 1999, sequence number are the part continuation application of the U.S. Patent application of No.09/350415, and with submitted on June 30th, 1997, sequence number is that the U.S. Patent application of No.08/884192 is relevant, these two patent applications are all by with reference to being incorporated among the present invention.
Background technology of the present invention
The present invention relates to system and method that matrix is heat-treated.
The matrix treatment system is used to make logic semiconductor computing and memory device, flat-panel monitor, CD ROMs and miscellaneous equipment.In processing procedure, these matrixes will stand chemical vapor deposition (CVD) and rapid thermal treatment (RTP).RTP handles such as comprising rapid thermal annealing (RTA), Rapid Thermal cleaning (RTC), rapid heat chemical vapour deposition (RTCVD), rapid thermal oxidation (RTO) and Rapid Thermal Nitrided (RTN).The RTP system generally includes a heating element, and this heating element is made by one or more lamp, by an optical transmission window described matrix is carried out radiation heating.The RTP system can also comprise one or more other optical element, such as light reflective surface and one or more photodetector facing to the matrix trailing flank, is used in processing procedure the temperature of matrix being measured.Many rapid thermal treatment all need be that the basis is accurately controlled substrate temperature with time.
To general introduction of the present invention
Characteristics of the present invention are to have proposed a kind of heat treatment method, wherein, at heating period or cooling stage or simultaneously in these two stages, can control the temperature response of a matrix.This has just alleviated the hot polymerization collection (thermal budget) to matrix, and improves the quality and the performance of the device that is shaped on this matrix.Especially, the inventor has realized that the temperature response of matrix can be controlled by in heat treatment process the heat transfer rate of a matrix and a storage heater (such as a water-cooled reflecting plate device) being controlled.
In one aspect, described matrix is heated, and in heating process, change the heat transfer rate between the interior storage heater of matrix and heat treatment system according to a heating program.
Listed some advantage of the present invention below.If heating or cooldown rate in the heat treatment system inner base are very high, the effect of some heat treatment method (such as the method for ultra-thin joint (the ultra-shallow junctions) that be used to be shaped) can be improved so.By changing in heat treatment process in a matrix and the treatment chamber heat transfer rate between the storage heater, can optimization heating period or cooling stage or while in these two stages, the quality of producing equipment to improve.Temperature uniformity on the matrix also can be improved.
From the following description, comprise accompanying drawing and claims, it is cheer and bright that further feature and advantage will become.
Summary to accompanying drawing
Accompanying drawing 1 is the schematic side elevation of the part of a heat treatment system, includes a reflecting plate device and a fluid injection device.
Accompanying drawing 2A is a kind of flow chart that is used for method that matrix is handled.
Having comprised among the accompanying drawing 2B in spike annealing heat treatment process of using the nitrogen purge gas of spike annealing heat treatment (spikeanneal thermal process) process neutralization of a use helium purge gas, is the substrate temperature curve that draw out on the basis with time.
Accompanying drawing 2C is a schematic diagram chart, shows the substrate temperature uniformity that is used to carry out best cooling processing.
Accompanying drawing 3A and 3B are the decomposition views of reflecting plate device shown in the accompanying drawing 1 and fluid injection device.
Accompanying drawing 3C is the schematic plan of reflecting plate device shown in the accompanying drawing 1 and fluid injection device; Utilization has been shown in dotted line the feature of bottom reflecting plate.
Accompanying drawing 4 is schematic diagrames of a purge gas control system in the matrix treatment system shown in the accompanying drawing 1.
Accompanying drawing 5 is schematic plan of a kind of selectable fluid injection device.
Accompanying drawing 6A and 6B are respectively a kind of schematic side elevation and vertical views of a selectable fluid injection device part.
Accompanying drawing 7A and 7B are respectively a kind of schematic side elevation and vertical views of a selectable fluid injection device part.
Accompanying drawing 8A and 8B are respectively the schematic side elevation and the vertical views of another fluid injection device.
Describe in detail
Be used for system 10 that matrix 12 is handled with reference to 1, one in accompanying drawing, include a treatment chamber 14, this treatment chamber 14 is carried out radiation heating by a water-cooled heating lamp device 16 by a quartz window 18.The periphery of matrix 12 is provided a supporting role by a rotatable bracing frame 20, and this bracing frame 20 can be to be rotated up to the speed about 300rpm (revolutions per minute).Below matrix 12, be provided with a reflecting plate device 22, this reflecting plate device 22 is used as a storage heater, and has a light reflective surface facing to matrix 12 trailing flanks, in order to improve the effective emissivity of matrix 12.Between the top surface of matrix 12 and reflecting plate device 22, formed a reflecting and concave-cavity 15.In being designed to the system that 8 inches (200 millimeters) silicon wafers are handled, the diameter of reflecting plate device is approximately 8.9 inches, distance between the top surface of matrix 12 and reflecting plate device 22 is approximately 5 to 10 millimeters, and the distance between matrix 12 and the quartz window 18 is approximately 25 millimeters.Reflecting plate device 22 is installed on the water-cooled base 23, and this base 23 keeps an about temperature of 23 ℃ usually.
The temperature at place, specific region is measured by a plurality of temperature probes 24 on the matrix 12, and these temperature probes 24 are oriented to Different Diameter on the matrix is measured to the substrate temperature of position.From the inner light that receives of treatment chamber, described loophole 25,26 and 27 extends through the top surface of reflecting plate device 22 to temperature probe 24 by loophole 25,26 and 27.Treatment system 10 can have ten temperature probes 22 altogether, only shows three probes in accompanying drawing 1.Usually,, use five temperature probes, and, use seven temperature probes for 300 millimeters matrix for 200 millimeters matrix.
In the surface of reflecting plate, the diameter of each loophole can be approximately 0.08 inch.Sapphire light pipe will be sent to corresponding photodetector (such as pyrometer) by the light that loophole receives, and photodetector is used to detect the temperature at place, specific region on the matrix 12.Received by a controller 28 by the detected temperature of photodetector, this controller 28 is used to control the radiation output of heating lamp device 16; Formed feedback loop has improved the ability that treatment system evenly heats matrix 12.This control system is described in U.S. Patent No. 5755511, and this United States Patent (USP) has licensed to assignee of the present invention, and here by disclosed all the elements are incorporated among the present invention with reference to inciting somebody to action wherein.
As shown in the accompanying drawing 1, in some Technology for Heating Processing, can a kind of processing gas 39 be fed in the treatment chamber 14 by an air inlet 30.Handle gas stream and cross the top surface of matrix 12, and react, in order to such as forming an oxide layer or a nitration case with matrix after the heating.Unnecessary processing gas, and any volatile reaction by-product (such as the oxide that is produced by matrix) are taken away from treatment chamber 14 by gas outlet 32 under the effect of a pumping system 34.In other Technology for Heating Processing, a kind of purge gas (such as nitrogen) can be fed in the thermal processing chamber 14 by air inlet 30.Purge gas flows through the top surface of matrix 12, in order to carry away the volatile impurity in the treatment chamber 14.
In reflecting and concave-cavity 15, make a kind of purge gas 42 on the top surface of reflecting plate device 22, form laminar flow basically by a washing fluid injection device 40.Purge gas 42 is removed in reflecting and concave-cavity 15 by an exhaust outlet 44, and the diameter of described exhaust outlet 44 is approximately 0.375 inch, and is configured to be approximately 2 inches with the distance of reflecting plate device 22 central axis.In the course of the work, purge gas is injected in the purge gas input unit 46, and distributes by a plurality of passages 48 on the reflecting plate device 22.Subsequently, purge gas is led to a baffler 50, and this baffler 50 is positioned at the top surface top of reflection unit 22 at a certain distance, and gap ratio is as being approximately 0.01 inch (0.25 millimeter), so that purge gas 42 forms laminar flow basically.
With reference to accompanying drawing 2A and 2B, in one embodiment, a ultra-thin joint can be as described as follows be shaped on a semiconductor substrate that contains impurity.Matrix is loaded onto in the thermal processing chamber 14 (step 200).First kind of purge gas (such as nitrogen) is fed in the thermal processing chamber 14 by air inlet 30, and perhaps the outlet by washing fluid injection device 40 is fed in the reflecting and concave-cavity 15, perhaps carries out simultaneously (step 202).Utilize heating lamp device 16 that matrix is heated to an initial temperature (step 204) that is approximately 700 ℃.At time t
0The place, heating lamp device 16 begins matrix is heated to a target peak temperature (step 206) such as about 1000 ℃ or 1100 ℃.Matrix with after being heated to a temperature that corresponds essentially to described target peak temperature (at time t
1The place), the emittance of being supplied with by heating lamp device 16 reduces, and by washing fluid injection device 40 second kind of purge gas (such as helium) is fed in the reflecting and concave-cavity 15 (step 208).In practice, the helium purge gas can begin feed just before target temperature reaches, and when being heated to target temperature with convenient matrix, was full of second kind of purge gas in the reflecting and concave-cavity 15 that forms between matrix and reflection unit 22.If first kind of purge gas carries out feed by washing fluid injection device 40 in the heating period, so at time t
1Perhaps near time t
1The purge gas of place's feed is converted to second kind of purge gas by first kind of purge gas.Be cooled to one (such as below 800 ℃) below the threshold temperature afterwards at matrix, matrix is taken out (step 210) from thermal processing chamber 14.
When about 1 to 3 second that reaches before the target temperature, second kind of purge gas is fed into reflecting and concave-cavity 15.Ideally, when about 1 to 2 second that reaches before the target temperature, begin second kind of cleaned gas stream of feed, perhaps when about 1 to 1.5 second that reaches before the target temperature, begin second kind of cleaned gas stream of feed.The actual time period is determined (referring to accompanying drawing 4) according to the system that is used for second kind of purge gas imports in the reflecting and concave-cavity.
If in reflecting and concave-cavity 15, have first kind of purge gas, stop feed along with first kind of cleaned gas stream so and from reflecting and concave-cavity, discharge via exhaust outlet 44, second kind of purge gas will replace first kind of purge gas in reflecting and concave-cavity 15.
Second kind of purge gas can be imported in the reflecting and concave-cavity 15 at heat treated cooling stage.Such as, in another embodiment, second kind of purge gas can be fed in the reflecting and concave-cavity 15 at the cooling stage after the soaking stage of Technology for Heating Processing.
The inventor has realized that, by the heating period in heat treatment process or cooling stage or the heat transfer rate of while between matrix of these two phasic changes and the inner storage heater of treatment chamber, can improve to optimization the quality of institute's producing equipment.
For example, by selecting to be fed into the purge gas between matrix 12 and the treatment system 10 inner described storage heaters (such as water-cooled reflecting plate device 22) suitably, can obviously improve the cooldown rate of matrix.In one aspect, the inventor has realized that, purge gas (such as the combination of helium, hydrogen or these gases) with relative high thermal conductivity can improve the cooldown rate of matrix, thus and the operating characteristic or the treatment effeciency of raising particular device (such as ultra-thin (ultra-shallow) junction transistor).For example, and compare when using a kind of purge gas (such as nitrogen) that has than low thermal conductivity, in the time of in the helium purge gas is fed to reflecting and concave-cavity 15, the cooldown rate of matrix obviously increases.As shown in the accompanying drawing 2B, at time t
1With t
2Between (can be the magnitude in about 6 seconds), utilize the helium purge gas substrate temperature can be cooled to about 650 ℃ from about 1100 ℃, and utilize the nitrogen purge gas in the identical time, only substrate temperature can be cooled to 800 ℃.On the other hand, the inventor has realized that, a kind of purge gas with relatively low conductive coefficient (such as two or more combination in nitrogen, argon gas, xenon or these gas) can be fed in the reflecting and concave-cavity 15, comes heating period in Technology for Heating Processing (such as the time t among the accompanying drawing 2B
0And t
1Between), increase the speed that substrate temperature raises by thermal coupling (thermallycoupling) phenomenon that reduces between matrix 12 and the reflecting plate device 22.Therefore, be fed into purge gas between matrix and the storage heater by being chosen at heating and cooling stage in the Technology for Heating Processing suitably, overall hot polymerization collection will reduce, and described hot polymerization collection is the integration of a substrate temperature T (t) and a set time section: ∫ T (t) dt.This will improve the quality of utilizing the particular device that this Technology for Heating Processing produces.
For most effective cooldown rate, must optimize the speed (standard litres of per minute (slm)) that second kind of purge gas (such as helium) discharged from reflecting and concave-cavity.If the gas rate of discharge is excessive, the helium purge gas will flow out from chamber too quickly so, stops between matrix and reflecting plate device the thermal coupling phenomenon to take place effectively.On the other hand, if deflation rate is too small, the helium purge gas needs the long time could arrive the central region of matrix, can cause the circumferential section of matrix to cool off fast.This will produce huge thermal stress, causes matrix is exerted an influence.
The speed that second kind of purge gas is injected in the reflecting and concave-cavity preferably is approximately equal to the speed that this gas is discharged from reflecting and concave-cavity.The inventor has been found that this can obviously alleviate the thermal gradient on the matrix in the cooling down operation process, be suppressed at and form defective in the matrix.
Also have, the inventor has been found that the second kind of purge gas that flows in the reflecting and concave-cavity in cooling procedure, preferably such as fast as much as possible in the spike annealing operating process.This will guarantee maximum moment fall off rate, Max dT/dt (℃/second), and matrix is in the time under the target temperature, it is optimized forming shape technology for ultra-thin face.
As shown in the table 1, when the charge velocity of second kind of purge gas equates basically with rate of discharge (F is capable), the temperature uniformity in cooling procedure on the matrix (the Max Δ (℃)) be best.What described Max Δ was data represented is that these five photodetectors are used for substrate temperature being measured to the position five Different Diameter by the maximum temperature reading of five photodetectors generations and the difference between the minimum temperature reading.Just as can be seen, when purge gas that the purge gas that flows into is substantially equal to flow out, Max Δ minimum, so the temperature uniformity on the matrix is in best condition.
Described data also show, when flowing of second kind of purge gas is higher relatively (F is capable), maximum moment fall off rate and time (time>1000 ℃ (s)) of being under the target temperature of matrix be best.That is to say that when purge gas flowing in reflecting and concave-cavity was higher relatively, the time that matrix is under the target temperature was minimum.
Table 1
OK | Chamber pressure (torr) | Gas injects (slm) | Gas is discharged (slm) | Time>1000 ℃ (s) | Max dt/dt (℃/s) | MaxΔ (℃) |
A | 770 | 15 | 7.5 | 2 | >80 | 13 |
B | 770 | 15 | 9.5 | 2 | >80 | 10 |
C | 770 | 10 | 9.5 | 2.2 | >80 | 10 |
D | 770 | 10 | 7.5 | 2.1 | >80 | 13 |
E | 800 | 15 | 15 | 2 | >80 | 6 |
F | 850 | 20 | 20 | <1.7 | 85 | 3 |
Accompanying drawing 2C compares some data among the extremely capable F of capable A with graph mode.What curve A A and AB represented is the temperature reading that is positioned at the photodetector at matrix middle part and matrix border place among the row A, and curve FA and FB representative is to be positioned in the middle part of the matrix and the temperature reading of the photodetector at matrix border place among the row F.Curve A C and FC show the temperature uniformity (Max Δ) on the matrix among capable A and the row F.Just as can be seen, when the inflow of second kind of purge gas was substantially equal to the outflow of second kind of purge gas, temperature uniformity was best.
With reference to accompanying drawing 3A and 3B, in an embodiment who cleans reflector 40 (purge reflector), reflecting plate device 22 includes a guide ring 52, a top reflecting plate 54 and a bottom reflecting plate 56.Bottom reflecting plate 56 has a horizontal channel 58, is used for receiving purge gass from gas input device 46, and is used for purge gas is delivered to a Vertical Channel 60, and this Vertical Channel 60 is connected with a plurality of horizontal channels 48 on the top reflecting plate 54.Horizontal channel 48 is used for purge gas is assigned to the diverse location place of top reflecting plate 54 circumference.Guide ring 52 includes a circumferential side wall 62, this circumferential side wall 62 rests against on the lower peripheral edge 64 of bottom reflecting plate 56, and circumferential side wall with top reflecting plate 54, formed 0.0275 inch wide Vertical Channel, this Vertical Channel is used for cleaned gas stream is directed to air deflector 50, makes purge gas form laminar flow basically on the top surface of reflecting plate 54.By exhaust outlet 44 purge gas and entrained any volatile impurity are removed from treatment chamber.A horizontal channel 66 on the bottom reflecting plate 56 receives waste gas from exhaust outlet 44, and waste gas is directed in the pipeline 68, and this pipeline 68 is connected on the pumping system.Each passage 48,58 and 60 cross-sectional flow area all can be approximately 0.25 inch * 0.1 inch.
With reference to accompanying drawing 3C, a kind of purge gas can import in the reflecting and concave-cavity 15 at the circular arc of the top surface place of top reflecting plate 54 about 75 degree along.The laminar flows that finally formed basically by purge gas 42 extend on a zone of top reflecting plate 54 top surfaces, and this zone is corresponding to 75 covering of the fans 70 of spending, and include on the top reflecting plate 54 nine (comprising loophole 25,26 and 27) in ten loopholes.In the aforementioned embodiment, a kind of purge gas 42 of high thermal conductivity coefficient (such as helium or hydrogen) has improved cooling stage in rapid thermal treatment (such as the time t in accompanying drawing 2B
1And t
2Between), the heat conduction between matrix 12 and the reflection unit 22.
The flow velocity of purge gas and processing gas is controlled by the fluid control systems shown in the accompanying drawing 4.A mass flow controller 80 is used for the gas flow rate that enters into by air inlet 30 in the treatment chamber 14 is adjusted, and a pressure sensor 82 and a pressure-control valve 84 are used for the gas flow rate of removing from treatment chamber 14 by gas outlet 32 is adjusted.Purge gas is guided in the reflecting and concave-cavity 15 by gas input device 46, and gas input device 46 is connected on the filter 86.A mass flow controller 88 is used for the cleaned gas stream that enters into by purge gas injection device 40 in the reflecting and concave-cavity 15 is adjusted.An adjustable flow restrictor 90 and a mass flow controller 92 are used for the purge gas flow velocity of removing from reflecting and concave-cavity 15 is adjusted.In order to reduce the purge gas in the processing region of transferring in the reflecting and concave-cavity 15, above matrix 12, flow restrictor 90 is regulated, and the purge gas flow velocity in being imported into reflecting and concave-cavity 15 is substantially equal to remove the flow velocity of purge gas from reflecting and concave-cavity 15.Solenoid break valve 94 and 96 provides additionally to be controlled by the mobile of reflecting and concave-cavity 15 purge gas.Although the flow velocity of purge gas can change according to the internal pressure of reflecting and concave-cavity 15 and the pumpability of pumping system 34, but be designed to handle in the system of eight inches (200 millimeters) silicon wafers at one, purge gas can be crossed reflecting and concave-cavity 15 with the data rate stream of about 9 to 20slm (standard litres of per minute).The internal pressure of reflecting and concave-cavity 15 and treatment chamber 14 can be about 850 torrs.
Purge gas can be fed in the reflecting and concave-cavity 15 with multitude of different ways.
With reference to accompanying drawing 5, in one embodiment, a reflecting plate device 100 is similar in construction to reflecting plate device 22, except the diverse location that this reflecting plate device 100 is designed on top reflecting plate 104 whole circumference is introduced a kind of purge gas 102.Purge gas 102 is removed by an exhaust outlet 106, and this exhaust outlet 106 extends through top reflecting plate 104.Purge gas 102 can be guided and the about 4.33 inches position of reflecting plate 104 Center Gap, and exhaust outlet 106 can be placed in and the about 2 inches position of reflecting plate 104 Center Gap.When distributing on the whole surface of loophole 108 at reflecting plate 104, can use present embodiment.
With reference to accompanying drawing 6A and 6B, in another embodiment, a reflecting plate device 110 also is similar in construction to reflecting plate device 22, except this reflecting plate device 110 includes a baffler 112 and top reflecting plate 114, described baffler 112 limits a plurality of flow channels jointly with top reflecting plate 114, is used for forming laminar flow at the circumferential area 116 to 122 around loophole 124 and 126 basically by purge gas.Purge gas flows through the vertical circular passage 128 and 129 in the top reflecting plate 114.Purge gas can be discharged by an exhaust outlet (not shown), and described exhaust outlet extends through top reflecting plate 114; Purge gas also can optionally be discharged into the circumferential edges top of reflecting plate device 110.In the present embodiment, the top surface of baffler 112 is as main light reflective surface, and this light reflective surface is facing to the trailing flank of matrix.Baffler 112 can be positioned at the top of top reflecting plate 114 with the distance of 0.01 inch (0.25 millimeter).
With reference to accompanying drawing 7A and 7B, in another embodiment, a reflecting plate device 130 includes a Vertical Channel 132, be used to receive cleaned gas stream, with a grooving shape air deflector 134, be used for cleaned gas stream 136 is carried out deflection, across the rectangle heavy curtain of loophole 138, described loophole 138 extends through a reflecting plate 140 as same.A grooving shape exhaust outlet 142 is used to remove purge gas 136.Air deflector 134 can be positioned at the top surface top of reflecting plate 140 with the distance of about 0.01 inch (0.25 millimeter).
As shown in accompanying drawing 8A and the 8B, in another embodiment, a reflecting plate device 150 can include a plurality of apertures 152,154,156, and they all are connected on the shared air chamber 158, and this shared air chamber 158 correspondingly is connected on the purge gas inlet port 160.Aperture 152 to 156 is arranged into and can purge gas be directed in the reflecting and concave-cavity that is formed between matrix 12 and the reflecting plate device 150 equably.Aperture 152 to 156 also is arranged into the position that is adapted to loophole 25 to 27, and temperature probe 24 receives the light that is sent by matrix 12 by described loophole 25 to 27.In the course of the work, purge gas flow in the reflecting and concave-cavity with about flow velocity of 9 to 20slm; On the whole, flow velocity must be less than matrix 12 is raised up required speed from bracing frame 20.Purge gas is removed from reflecting and concave-cavity by an exhaust outlet 164 under the effect of a pumping system 162.
Also may have other purge gas conveying system.For example, purge gas can be that the rotary gas delivery system of describing in the U.S. Patent application of No.09/287947 carries out feed by sequence number, the applying date of described U.S. Patent application is on April 7th, 1999, exercise question is " be used for equipment and method that matrix is heat-treated ", here by being incorporated by reference among the present invention.
Other embodiment all are positioned within the protection range of claim.
For example, although the disclosed embodiment in front is described with reference to a storage heater (such as reflecting plate device 22) unique, that temperature is relatively low, also can be other storage heater structures.Storage heater can be placed in the diverse location place of heat treatment system 10 inside.Two or more independently storage heaters can be provided.Storage heater can include a surface that temperature is higher relatively, and different purge gass can be fed in the reflecting and concave-cavity 15, and this reflecting and concave-cavity 15 is formed between storage heater and the matrix, controls the temperature response of matrix.In certain embodiments, the temperature of storage heater can change in heat treatment process, in order to improve the temperature response of matrix.
In another embodiment, the heat transfer rate between storage heaters of a matrix and treatment system 10 inside can be optimized by the emissivity that changes storage heater in heat treatment process.For example, the top surface of reflecting plate device 22 can include a chromium electroplated coating, and the reflectivity of this chromium electroplated coating can selectively changing take place by the voltage that change puts on the coating.In the course of the work, the reflectivity of reflecting plate device 22 can maximize the heating period in heat treatment process, and can minimize at cooling stage.By this way, the heat transfer rate between matrix and the reflecting plate device 22 can reduce in the heating period, and increased at cooling stage.
In another embodiment, the heat transfer rate between storage heaters of a matrix and treatment system 10 inside can be optimized by the spacing that changes between matrix and the storage heater.For example, bracing frame 20 can be configured to move up and down with respect to the top surface of reflecting plate device 22.In one embodiment, in the course of the work, bracing frame 20 can be in heat treatment process heating period matrix is placed one relatively away from the position of reflecting plate device 22, and the cooling stage that bracing frame 20 can be in heat treatment process places one relatively near the position of reflecting plate device 22 with matrix.By this way, the heat conductivility between matrix and the reflecting plate device 22 can reduce the heating period in heat treatment process, and can increase by the cooling stage in heat treatment process, to improve the quality of institute's producing equipment on matrix.
In another embodiment, the heat transfer rate between storage heaters of a matrix and treatment system 10 inside can be optimized by the pressure that changes purge gas between matrix and the storage heater in heat treatment process.For example, the heating period in heat treatment process, the pressure of purge gas can be reduced to and be lower than atmospheric pressure (such as 1 to 5 torr), and the cooling stage in heat treatment process, pressure can increase to atmospheric pressure (770 torr).The component of purge gas also can change in heat treatment process.For example, in the heating period, purge gas can be made up of nitrogen, and at cooling stage, purge gas can be made up of helium.
Control for temperature response in rapid thermal treatment process, disclose some system and methods matrix.The present invention can produce the particular device (such as ultra-thin junction transistor) with operating characteristic of improving through the physical characteristic and the process of improvement.
Claims (34)
1. one kind is used for the method for in a heat treatment system matrix being heat-treated, described heat treatment system comprises lamp and reflecting surface of an array that points to described matrix first side, it is spaced apart with second side of described matrix and connect with a storage heater that described reflecting surface passes a reflecting and concave-cavity, and described method comprises:
According to the lamp of a heating program matrix is heated with described array; With
In the heating program, change the heat transfer rate that passes described reflecting and concave-cavity between matrix and this storage heater.
2. the method described in claim 1 is characterized in that: change the speed that heat is transmitted in the heating program by changing the conductive coefficient that passes described reflecting and concave-cavity between described matrix and the storage heater.
3. the method described in claim 2 is characterized in that: change conductive coefficient by changing the characteristic that is arranged in the heat transmission medium of described reflecting and concave-cavity in described heating program.
4. the method described in claim 3, it is characterized in that: described heat transmission medium includes a kind of purge gas, and changes conductive coefficient by the component that changes purge gas in the heating program.
5. the method described in claim 3, it is characterized in that: described heat transmission medium includes a kind of purge gas, and the purge gas pressure in described reflecting and concave-cavity changes conductive coefficient in the heating program by changing.
6. the method described in claim 1 is characterized in that: at the cooling stage of heating program, the conductive coefficient between described matrix and the reflecting surface increases.
7. the method described in claim 1, it is characterized in that: the heating period in the heating program, first kind of purge gas is fed to described reflecting and concave-cavity, and the cooling stage in the heating program, second kind of purge gas is fed to described reflecting and concave-cavity, and the conductive coefficient of second kind of purge gas is greater than the conductive coefficient of first kind of purge gas.
8. the method described in claim 7, it is characterized in that: first kind of purge gas is selected from nitrogen, argon gas and xenon, and second kind of purge gas is selected from helium and hydrogen.
9. the method described in claim 1 is characterized in that: in the heating program, change heat transfer rate by the emissivity that changes described storage heater surface.
10. the method described in claim 1 is characterized in that: in the heating program, change the speed that heat is transmitted by the distance that changes between described matrix and the storage heater.
11. one kind is used for the method for in a heat treatment system matrix being heat-treated, described heat treatment system comprises the lamp of an array that points to described matrix, and described method comprises:
Matrix is heated with described lamp according to a heating program; And
In the part of described heating program, first kind of purge gas is fed in this heat treatment system;
In the second portion of described heating program, second kind of purge gas is fed in this heat treatment system, described second kind of purge gas is different with first kind of purge gas.
12. the method described in claim 11 is characterized in that: the cooling stage of second kind of purge gas in described heating program is fed in the heat treatment system.
13. the method described in claim 12 is characterized in that: be heated to a target peak temperature or during near this target peak temperature, second kind of purge gas is fed in the heat treatment system in the temperature of described matrix.
14. the method described in claim 13 is characterized in that: when the temperature of described matrix descended, second kind of purge gas was fed in the heat treatment system.
15. the method described in claim 13 is characterized in that: the heating period in described heating program, first kind of purge gas is fed in the heat treatment system.
16. the method described in claim 11 is characterized in that: the conductive coefficient of second kind of purge gas is greater than the conductive coefficient of first kind of purge gas.
17. the method described in claim 16 is characterized in that: second kind of purge gas includes helium or hydrogen, perhaps comprises helium and hydrogen simultaneously.
18. the method described in claim 16 is characterized in that: first kind of purge gas includes nitrogen, and includes helium in second kind of purge gas.
19. the method described in claim 11 is characterized in that: second kind of purge gas is fed in described matrix surface and the heat treatment system in the heat treatment system between the storage heater.
20. the method described in claim 19 is characterized in that:
Heating period in described heating program, first kind of purge gas is fed between interior described matrix surface of heat treatment system and the storage heater, and
Cooling stage in described heating program, second kind of purge gas is fed between interior described matrix surface of heat treatment system and the storage heater.
21. one kind is used for the method for in a heat treatment system matrix being heat-treated, comprises:
First kind of purge gas is fed in this heat treatment system;
Matrix is heated to a target temperature; And
Be heated to target temperature or during near target temperature, second kind of purge gas be fed in this heat treatment system at substrate temperature, the conductive coefficient of this second kind of purge gas is greater than the conductive coefficient of first kind of purge gas.
22. the method described in claim 21 is characterized in that: second kind of purge gas includes helium.
23. the method described in claim 22 is characterized in that: first kind of purge gas includes nitrogen.
24. the method described in claim 21 is characterized in that: be heated to target temperature or during near target temperature, stopped first kind of purge gas of feed in the heat treated system at described matrix.
25. one kind is used for the method for in a heat treatment system matrix being heat-treated, comprises:
Matrix is heated to a target temperature; With
Be heated to target temperature or during at matrix near target temperature, begin a kind of purge gas is fed in matrix surface and this heat treatment system in the heat treatment system between the storage heater, described purge gas is used to increase the conductive coefficient between matrix surface and the storage heater, wherein, described purge gas is fed in the described heat treatment system at the cooling stage of a heating program.
26. the method described in claim 25 is characterized in that: described purge gas includes helium.
27. the method described in claim 25 is characterized in that: during 1 to 3 second before described matrix is heated to target temperature, described purge gas is fed in the heat treatment system.
28. the method described in claim 25 is characterized in that: during 1 to 2 second before described matrix is heated to target temperature, described purge gas is fed in the heat treatment system.
29. the method described in claim 25 is characterized in that: during 1 to 1.5 second before described matrix is heated to target temperature, described purge gas is fed in the heat treatment system.
30. one kind is used for the method for in a heat treatment system matrix being heat-treated, comprises:
First kind of purge gas is fed in this heat treatment system;
Matrix is heated to a target temperature; With
Be heated to target temperature or during at matrix near target temperature, second kind of purge gas is fed in matrix surface and this heat treatment system in the heat treatment system between the storage heater, and the conductive coefficient of described second kind of purge gas is greater than the conductive coefficient of first kind of purge gas.
31. the method described in claim 30 is characterized in that: described first kind of purge gas includes nitrogen, and second kind of purge gas includes helium.
32. the method described in claim 30 is characterized in that: be heated to target temperature or during near target temperature, stop first kind of purge gas of feed in the heat treated system at described matrix.
33. the method described in claim 32 is characterized in that: second kind of purge gas is fed in the heat treatment system with a higher relatively flow velocity, with so that the time that described matrix is under the target temperature minimum.
34. the method described in claim 30 is characterized in that: when the temperature of described matrix descended, second kind of purge gas was fed in the heat treatment system.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/611,349 US6803546B1 (en) | 1999-07-08 | 2000-07-06 | Thermally processing a substrate |
US09/611,349 | 2000-07-06 |
Publications (2)
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CN1447980A CN1447980A (en) | 2003-10-08 |
CN1279577C true CN1279577C (en) | 2006-10-11 |
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CNB018144985A Expired - Lifetime CN1279577C (en) | 2000-07-06 | 2001-07-03 | Thermally processing substrate |
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EP (1) | EP1297560A2 (en) |
JP (1) | JP2004503108A (en) |
KR (1) | KR100838874B1 (en) |
CN (1) | CN1279577C (en) |
WO (1) | WO2002005323A2 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US6803546B1 (en) * | 1999-07-08 | 2004-10-12 | Applied Materials, Inc. | Thermally processing a substrate |
JP5719710B2 (en) * | 2011-07-11 | 2015-05-20 | 株式会社ニューフレアテクノロジー | Vapor growth apparatus and vapor growth method |
US8980767B2 (en) * | 2012-01-13 | 2015-03-17 | Applied Materials, Inc. | Methods and apparatus for processing a substrate |
US10770309B2 (en) | 2015-12-30 | 2020-09-08 | Mattson Technology, Inc. | Features for improving process uniformity in a millisecond anneal system |
KR102010329B1 (en) * | 2017-08-04 | 2019-10-15 | 주식회사 디엠에스 | Substrate processing apparatus and in line type substrate processing system using the same |
JP7018825B2 (en) * | 2018-06-05 | 2022-02-14 | 東京エレクトロン株式会社 | Film formation method and film formation equipment |
CN114045470B (en) * | 2021-12-31 | 2022-09-30 | 西安奕斯伟材料科技有限公司 | Cleaning method for normal-pressure epitaxial reaction chamber and epitaxial silicon wafer |
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Publication number | Priority date | Publication date | Assignee | Title |
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JPS62282437A (en) * | 1986-05-31 | 1987-12-08 | Shinku Riko Kk | Rapid heating and cooling device for semiconductor wafer treatment |
US4818327A (en) * | 1987-07-16 | 1989-04-04 | Texas Instruments Incorporated | Wafer processing apparatus |
JP2635153B2 (en) * | 1989-03-15 | 1997-07-30 | 株式会社日立製作所 | Vacuum processing method and device |
US5620525A (en) * | 1990-07-16 | 1997-04-15 | Novellus Systems, Inc. | Apparatus for supporting a substrate and introducing gas flow doximate to an edge of the substrate |
US5181556A (en) * | 1991-09-20 | 1993-01-26 | Intevac, Inc. | System for substrate cooling in an evacuated environment |
TW277139B (en) * | 1993-09-16 | 1996-06-01 | Hitachi Seisakusyo Kk | |
US5676205A (en) * | 1993-10-29 | 1997-10-14 | Applied Materials, Inc. | Quasi-infinite heat source/sink |
US5620560A (en) * | 1994-10-05 | 1997-04-15 | Tokyo Electron Limited | Method and apparatus for heat-treating substrate |
US6046439A (en) * | 1996-06-17 | 2000-04-04 | Mattson Technology, Inc. | System and method for thermal processing of a semiconductor substrate |
NL1003538C2 (en) * | 1996-07-08 | 1998-01-12 | Advanced Semiconductor Mat | Method and device for contactless treatment of a disc-shaped semiconductor substrate. |
US5834068A (en) * | 1996-07-12 | 1998-11-10 | Applied Materials, Inc. | Wafer surface temperature control for deposition of thin films |
JPH10172977A (en) * | 1996-12-11 | 1998-06-26 | Sumitomo Electric Ind Ltd | Heat treatment method and its device for compound semiconductor substrate |
JP2000505961A (en) * | 1996-12-20 | 2000-05-16 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Furnace for rapid heat treatment |
JPH10199824A (en) * | 1997-01-14 | 1998-07-31 | Japan Storage Battery Co Ltd | Ultraviolet treating apparatus |
US6054688A (en) * | 1997-06-25 | 2000-04-25 | Brooks Automation, Inc. | Hybrid heater with ceramic foil serrated plate and gas assist |
JP4625183B2 (en) * | 1998-11-20 | 2011-02-02 | ステアーグ アール ティ ピー システムズ インコーポレイテッド | Rapid heating and cooling equipment for semiconductor wafers |
US6803546B1 (en) * | 1999-07-08 | 2004-10-12 | Applied Materials, Inc. | Thermally processing a substrate |
NL1013938C2 (en) * | 1999-12-23 | 2001-06-26 | Asm Int | Device for treating a wafer. |
JP2001297995A (en) * | 2000-04-13 | 2001-10-26 | Nec Corp | Manufacturing method of circuit and manufacturing device of circuit |
JP2001308023A (en) * | 2000-04-21 | 2001-11-02 | Tokyo Electron Ltd | Equipment and method for heat treatment |
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- 2001-07-03 WO PCT/US2001/021154 patent/WO2002005323A2/en active Application Filing
- 2001-07-03 CN CNB018144985A patent/CN1279577C/en not_active Expired - Lifetime
- 2001-07-03 KR KR1020037000152A patent/KR100838874B1/en not_active IP Right Cessation
- 2001-07-03 EP EP01952404A patent/EP1297560A2/en not_active Withdrawn
- 2001-07-03 JP JP2002508836A patent/JP2004503108A/en active Pending
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JP2004503108A (en) | 2004-01-29 |
CN1447980A (en) | 2003-10-08 |
KR20030014322A (en) | 2003-02-15 |
KR100838874B1 (en) | 2008-06-16 |
WO2002005323A3 (en) | 2002-06-20 |
WO2002005323A2 (en) | 2002-01-17 |
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