WO2014034217A1 - 基板処理方法および基板処理装置 - Google Patents
基板処理方法および基板処理装置 Download PDFInfo
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- WO2014034217A1 WO2014034217A1 PCT/JP2013/065778 JP2013065778W WO2014034217A1 WO 2014034217 A1 WO2014034217 A1 WO 2014034217A1 JP 2013065778 W JP2013065778 W JP 2013065778W WO 2014034217 A1 WO2014034217 A1 WO 2014034217A1
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- Prior art keywords
- substrate
- dopant
- liquid
- hydrofluoric acid
- thin film
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 308
- 238000000034 method Methods 0.000 title claims description 70
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 271
- 239000007788 liquid Substances 0.000 claims abstract description 268
- 239000002019 doping agent Substances 0.000 claims abstract description 215
- 239000010409 thin film Substances 0.000 claims abstract description 107
- 239000010408 film Substances 0.000 claims abstract description 72
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims description 163
- 230000008569 process Effects 0.000 claims description 57
- 238000003672 processing method Methods 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 20
- 238000007654 immersion Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 34
- 239000010703 silicon Substances 0.000 abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 110
- 230000007246 mechanism Effects 0.000 description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 32
- 239000007789 gas Substances 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000012535 impurity Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 230000002093 peripheral effect Effects 0.000 description 7
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- QGLVEAGMVUQOJP-UHFFFAOYSA-N prop-2-enylboronic acid Chemical compound OB(O)CC=C QGLVEAGMVUQOJP-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000005468 ion implantation Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- 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
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
- H01L21/2251—Diffusion into or out of group IV semiconductors
- H01L21/2252—Diffusion into or out of group IV semiconductors using predeposition of impurities into the semiconductor surface, e.g. from a gaseous phase
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- 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
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
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- 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
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- H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
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- 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
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- H01L21/67075—Apparatus for fluid treatment for etching for wet etching
- H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
Definitions
- the present invention relates to a substrate processing method and a substrate processing apparatus for forming a thin film containing a dopant such as boron on the surface of a substrate such as a silicon semiconductor wafer.
- impurities are generally introduced by ion implantation and subsequent annealing.
- the ion implantation method is a technique in which impurity elements such as boron (B), arsenic (As), and phosphorus (P) are ionized and collided with a silicon semiconductor substrate at a high acceleration voltage to physically implant impurities ( For example, see Patent Document 1).
- the implanted impurities are activated by annealing.
- the conventional ion implantation method When introducing impurities, the conventional ion implantation method has an advantage that the implantation depth and concentration of impurities can be easily controlled.
- impurities in recent years, with the further miniaturization of semiconductor devices, it has been required to introduce impurities only into a very shallow region (a depth of several nm or less) on the surface layer of the substrate. It is difficult for the ion implantation method to accurately implant impurities only in such an extremely shallow surface layer region.
- impurities must be introduced into the uneven three-dimensional pattern, and in the ion implantation method in which ions collide from one direction, the impurities are uniformly introduced over the entire surface of the uneven pattern. It is difficult.
- Non-Patent Document 1 a technology that introduces impurities only in a very shallow region of the substrate surface by forming a monomolecular layer containing a dopant on the surface of the silicon substrate by wet processing and diffusing the dopant into the substrate surface layer by subsequent heat treatment is studied.
- impurities can be introduced only into a very shallow region of the surface layer of the substrate.
- a monomolecular layer containing a dopant is formed by a wet process, it is possible to introduce impurities evenly over the entire surface of a complex uneven pattern.
- Non-Patent Document 1 after the natural oxide film is removed with hydrofluoric acid, hydrogen termination treatment is performed in order to stabilize the surface state. Then, a hydrogen-terminated silicon substrate is supplied with a chemical solution containing a dopant to replace the hydrogen termination with a dopant, thereby forming a monomolecular layer containing the dopant. Thereafter, a cap film of silicon dioxide is formed, and a dopant is diffused on the substrate surface by performing a light irradiation heat treatment.
- Non-Patent Document 1 it takes a very long time (for example, 2.5 hours in Non-Patent Document 1) to form a monomolecular layer by the technique disclosed in Non-Patent Document 1. If such a long time is required for the process of forming the monomolecular layer, a practical throughput cannot be obtained.
- the present invention has been made in view of the above problems, and an object thereof is to provide a substrate processing method and a substrate processing apparatus capable of forming a thin film containing a dopant in a short time.
- a first aspect of the present invention is a substrate processing method for forming a thin film containing a dopant on a surface of a substrate, without performing hydrogen termination on the substrate from which the oxide film has been removed.
- a dopant liquid is supplied to the surface of the substrate to form a thin film containing the dopant.
- the oxide film removing step, the rinsing step, and the thin film forming step are successively executed.
- the oxide film removing step, the rinsing step, and the thin film forming step are performed in a non-atmospheric atmosphere.
- the fifth aspect is the substrate processing method according to the first aspect, wherein a mixed liquid of hydrofluoric acid and a dopant liquid is supplied to the surface of the substrate, and the oxide film formed on the surface is removed while the surface is removed. A thin film containing a dopant is formed.
- an oxide film removing step of supplying hydrofluoric acid to the surface of the substrate to remove the oxide film formed on the surface, and a dopant on the surface A thin film forming step of supplying a liquid to form a thin film, and starting the thin film forming step in the middle of the oxide film removing step.
- the thin film formed on the surface of the substrate by the dopant liquid is a monomolecular layer.
- a substrate processing apparatus for forming a thin film containing a dopant on the surface of the substrate, a chamber that accommodates the substrate, a holding unit that holds the substrate in the chamber, and a holding unit that holds the substrate.
- Hydrofluoric acid supplying means for supplying hydrofluoric acid to the surface of the substrate and removing the oxide film formed on the surface; rinsing liquid supplying means for supplying rinsing liquid to the surface of the substrate and washing away hydrofluoric acid; and A dopant liquid supply means for forming a thin film by supplying a dopant liquid to the surface of the substrate; and the hydrofluoric acid supply means for continuously supplying hydrofluoric acid, rinsing liquid, and dopant liquid to the surface; Control means for controlling the rinse liquid supply means and the dopant liquid supply means.
- a substrate processing apparatus for forming a thin film containing a dopant on the surface of a substrate, a chamber that accommodates the substrate, a holding unit that holds the substrate in the chamber, and a holding unit that holds the substrate.
- Hydrofluoric acid supplying means for supplying hydrofluoric acid to the surface of the substrate and removing the oxide film formed on the surface;
- dopant liquid supplying means for supplying a dopant liquid to the surface of the substrate to form a thin film;
- Control means for controlling the hydrofluoric acid supply means and the dopant liquid supply means so as to start supply of the dopant liquid in the middle of supplying hydrofluoric acid to the surface.
- the processing tank capable of storing the processing liquid and the immersion position immersed in the processing liquid stored in the processing tank.
- Holding means for holding the substrate hydrofluoric acid supply means for supplying hydrofluoric acid to the processing tank, rinsing liquid supply means for supplying a rinsing liquid to the processing tank, and dopant liquid supply for supplying a dopant liquid to the processing tank
- the hydrofluoric acid is supplied to the treatment tank and the hydrofluoric acid is stored, and then the rinse liquid is supplied to the treatment tank to replace the hydrofluoric acid with the rinse liquid.
- a control means for controlling the hydrofluoric acid supply means, the rinse liquid supply means, and the dopant liquid supply means so as to supply the dopant liquid to the treatment tank and replace the rinse liquid with the dopant liquid.
- the eleventh aspect is a substrate processing apparatus for forming a thin film containing a dopant on the surface of a substrate, a processing tank capable of storing a processing liquid, and an immersion position where the processing liquid is immersed in the processing liquid stored in the processing tank.
- the hydrofluoric acid supply means for supplying hydrofluoric acid to the treatment tank
- the dopant liquid supply means for supplying the dopant liquid to the treatment tank
- Control means for controlling the hydrofluoric acid supply means and the dopant liquid supply means so as to supply a mixed liquid of hydrofluoric acid and a dopant liquid to the treatment tank and store the mixed liquid.
- the thin film formed on the surface of the substrate by the dopant liquid is a monomolecular layer.
- a thin film containing a dopant by supplying a dopant liquid to the surface of the substrate without performing hydrogen termination on the substrate from which the oxide film has been removed from the surface. Therefore, the dopant is immediately bonded to the surface of the substrate without a process of replacing the hydrogen termination with the dopant, and a thin film containing the dopant can be formed in a short time.
- the dopant liquid is applied to the surface of the substrate that is not hydrogen-terminated. Will contact and a thin film containing a dopant can be formed in a short time.
- dopant liquid in order to start supply of dopant liquid in the middle of supplying hydrofluoric acid to the substrate surface, dopant liquid contacts the surface of the substrate which is not hydrogen-terminated.
- a thin film containing a dopant can be formed in a short time.
- a rinse liquid is supplied to a processing tank.
- the dopant liquid comes into contact with the surface of the substrate that is not hydrogen-terminated and contains the dopant.
- a thin film can be formed in a short time.
- the liquid mixture of hydrofluoric acid and a dopant liquid is supplied to a processing tank and the said liquid mixture is stored in the state which hold
- the monolayer thin film containing the dopant can be formed in a short time.
- FIG. 2 is a longitudinal sectional view of the substrate processing apparatus of FIG. 1 cut along the AA position. It is a flowchart which shows the process sequence in the substrate processing apparatus of FIG. It is a figure which shows the change of the surface state of a board
- FIG. 1 is a longitudinal sectional view of the substrate processing apparatus 1 according to the first embodiment cut along a plane parallel to the substrate W.
- FIG. 2 is a longitudinal sectional view of the substrate processing apparatus 1 of FIG. 1 cut along the AA position.
- the substrate processing apparatus 1 according to the first embodiment is a batch type apparatus that collectively performs surface treatment on a plurality of substrates W.
- the substrate processing apparatus 1 performs an oxide film removal process with hydrofluoric acid on a plurality of substrates W, then rinses the hydrofluoric acid from the surface of the substrate W with a rinsing liquid, and then the chemicals containing the dopant onto the surface of the substrate W. A monolayer thin film is formed.
- the substrate processing apparatus 1 mainly includes a chamber 10, a processing tank 14, a processing liquid supply mechanism 20, a lifter 30, a gas supply mechanism 35, an exhaust mechanism 40, and a control unit 49.
- the chamber 10 is a housing that accommodates the treatment tank 14, the lifter 30, and the like therein.
- the upper part 11 of the chamber 10 can be opened and closed by a sliding opening / closing mechanism (not shown). In a state where the upper part 11 is opened, a plurality of substrates W can be carried in and out from the opened part. Moreover, in the state which closed the upper part 11, the inside of the chamber 10 can be made into sealed space.
- the treatment tank 14 is a box-shaped container having a rectangular shape in plan view for storing a treatment liquid such as hydrofluoric acid (HF).
- a treatment liquid such as hydrofluoric acid (HF).
- Two rod-like discharge nozzles 16 are provided in the vicinity of the inner bottom of the processing tank 14.
- the two discharge nozzles 16 are provided in parallel to each other so that the longitudinal direction thereof is along the longitudinal direction of the processing tank 14.
- Each discharge nozzle 16 is formed with a plurality of discharge holes (not shown) at regular intervals along the longitudinal direction.
- the plurality of discharge holes are provided so as to be directed to the side of the substrate W immersed in the processing tank 14.
- the processing liquid is discharged obliquely upward from the two discharge nozzles 16 into the processing tank 14 as indicated by an arrow AR1.
- the “treatment liquid” is a generic name including hydrofluoric acid, a rinsing liquid, and a dopant liquid described later.
- the upper part of the processing tank 14 is opened, and an outer tank 15 is provided at the upper end of the outer wall surface of the processing tank 14 so as to surround it.
- the processing liquid discharged from the discharge nozzle 16 forms an upflow that flows upward in the processing tank 14 and overflows from the upper opening of the processing tank 14 to the outer tank 15.
- the processing liquid that has flowed into the outer tank 15 is discharged to the outside of the substrate processing apparatus 1 via the drainage line 17.
- a drain line 18 is connected to the bottom of the treatment tank 14, and a drain valve 19 is provided in the drain line 18. By opening the drain valve 19, the processing liquid stored in the processing tank 14 can be quickly drained.
- the treatment liquid supply mechanism 20 is a mechanism for supplying various treatment liquids into the treatment tank 14.
- the front end side of the supply pipe 21 of the processing liquid supply mechanism 20 is branched into two, and each is connected to the discharge nozzle 16.
- the proximal end side of the supply pipe 21 is branched into three and connected to a hydrofluoric acid supply source 22, a rinse liquid supply source 24, and a dopant liquid supply source 26, respectively.
- a hydrofluoric acid valve 23 is provided for a pipe connected to the hydrofluoric acid supply source 22, and a rinse liquid valve is provided for a pipe connected to the rinse liquid supply source 24.
- the pipe connected to the dopant liquid supply source 26 is provided with a dopant liquid valve 27, respectively.
- hydrofluoric acid is supplied from the hydrofluoric acid supply source 22 to the discharge nozzle 16, and hydrofluoric acid is supplied from the discharge nozzle 16 into the treatment tank 14.
- Hydrofluoric acid is an aqueous solution of hydrogen fluoride and has a property of corroding silicon dioxide (SiO 2 ).
- the concentration of hydrofluoric acid supplied by the hydrofluoric acid supply source 22 is set appropriately.
- the rinsing liquid valve 25 when the rinsing liquid valve 25 is opened, the rinsing liquid is supplied from the rinsing liquid supply source 24 to the discharge nozzle 16, and the rinsing liquid is supplied from the discharge nozzle 16 into the treatment tank 14.
- Alcohols are used as the rinsing liquid, and IPA (isopropyl alcohol) is used in the first embodiment.
- the alcohol used as the rinsing liquid is not limited to IPA, and may be ethanol.
- the dopant liquid valve 27 when the dopant liquid valve 27 is opened, the dopant liquid is supplied from the dopant liquid supply source 26 to the discharge nozzle 16, and the dopant liquid is supplied from the discharge nozzle 16 into the treatment tank 14.
- the dopant solution is a chemical solution containing a dopant, and has a property of forming a monolayer thin film containing the dopant on the surface by contacting the surface of the silicon substrate W.
- allylboronic acid pinacol ester containing boron (B) as a dopant is employed as the dopant liquid.
- any one of the hydrofluoric acid valve 23, the rinsing liquid valve 25, and the dopant liquid valve 27 may be opened selectively, or two or more may be opened simultaneously.
- the hydrofluoric acid valve 23 and the dopant liquid valve 27 are opened at the same time, the mixed liquid of hydrofluoric acid and the dopant liquid is supplied into the treatment tank 14.
- the lifter 30 is a mechanism that holds and lifts a plurality of substrates W, and includes a lifter head 31, three holding rods 32, and a lift drive unit 34.
- Each of the three holding rods 32 is extended from the lifter head 31 so that the longitudinal direction thereof is along the longitudinal direction of the processing tank 14 (that is, parallel to the discharge nozzle 16).
- a plurality of holding grooves (not shown) are formed in the holding bar 32 at predetermined intervals.
- the plurality of substrates W are collectively held in a standing posture (a posture in which the normal line of the substrate W faces the horizontal direction) by a plurality of holding grooves formed on the three holding rods 32. Further, the lifter head 31 is connected to the lift drive unit 34.
- a plurality of substrates W held by the three holding rods 32 by driving the elevating drive unit 34 is immersed in the processing liquid stored in the processing tank 14 (solid line position in FIG. 1) and processing. It is moved up and down between the pulling position above the tank 14 (the two-dot chain line position in FIG. 1). Note that the upper portion 11 of the chamber 10 is opened, and the raising / lowering drive unit 34 further raises the three holding rods 32 from the pulling position, thereby transferring the substrate W between the transfer robot outside the apparatus and the lifter 30. be able to.
- the gas supply mechanism 35 includes a pipe 36, a gas supply source 37, and a gas valve 38. By opening the gas valve 38, nitrogen gas (N 2 ) is supplied from the gas supply source 37 into the chamber 10.
- the exhaust mechanism 40 includes a pipe 41, an exhaust pump 42, and an exhaust valve 43. By opening the exhaust valve 43 while operating the exhaust pump 42, the atmosphere in the chamber 10 is exhausted to the outside of the apparatus.
- the exhaust pump 42 is a decompression pump. When the inside of the chamber 10 is a sealed space, the interior of the chamber 10 is a decompressed atmosphere below atmospheric pressure.
- the control unit 49 includes the various operation mechanisms (the hydrofluoric acid valve 23, the rinsing liquid valve 25, the dopant liquid valve 27, the gas valve 38, the exhaust valve 43, the exhaust pump 42, the lift drive unit 34) provided in the substrate processing apparatus 1. Etc.).
- the configuration of the control unit 49 as hardware is the same as that of a general computer. That is, the control unit 49 stores a CPU that performs various arithmetic processes, a ROM that is a read-only memory that stores basic programs, a RAM that is a readable and writable memory that stores various information, control software, data, and the like. It is configured with a magnetic disk.
- the processing in the substrate processing apparatus 1 proceeds by the CPU of the control unit 49 executing a predetermined processing program.
- FIG. 3 is a flowchart showing a processing procedure in the substrate processing apparatus 1.
- FIG. 4 is a diagram showing a change in the surface state of the substrate W accompanying the substrate processing. The processing procedure shown below proceeds by the control unit 49 controlling each operation mechanism of the substrate processing apparatus 1.
- a silicon dioxide natural oxide film 101 is formed on the surface of the silicon substrate W.
- the natural oxide film 101 is a silicon dioxide film inevitably formed when silicon exposed on the surface of the substrate W comes into contact with oxygen in the atmosphere.
- the surface of the substrate W is a main surface on which a device pattern is formed, and the back surface is a main surface on the opposite side.
- the plurality of substrates W held by the lifter 30 are lowered together, and the upper portion 11 of the chamber 10 is closed.
- the gas valve 38 is opened, and the exhaust valve 43 is opened while the exhaust pump 42 is operated to replace the inside of the chamber 10 with a nitrogen atmosphere.
- Subsequent surface treatment of the substrate W proceeds in a nitrogen atmosphere.
- the plurality of substrates W are lowered to the immersion position in the processing tank 14 by the lifter 30 and stopped. Accordingly, the plurality of substrates W are held at the immersion position in the processing tank 14 by the lifter 30.
- the hydrofluoric acid valve 23 is opened, and hydrofluoric acid is stored in the treatment tank 14. Further, hydrofluoric acid continues to be discharged from the discharge nozzle 16, and hydrofluoric acid continues to overflow into the outer tank 15 from the upper end of the processing tank 14. For this reason, the several board
- the substrate is formed on the surface of the substrate W by continuously supplying the hydrofluoric acid from the discharge nozzle 16 into the treatment tank 14 while maintaining the state in which the plurality of substrates W are immersed in the hydrofluoric acid stored in the treatment tank 14.
- the natural oxide film 101 of silicon dioxide is etched and removed (step S12). As a result, silicon is exposed on the surface of the substrate W, as shown in FIG.
- the hydrofluoric acid valve 23 is closed and the rinse liquid valve 25 is opened to discharge and supply the rinse liquid from the discharge nozzle 16 into the treatment tank 14.
- IPA is supplied as a rinse liquid.
- the rinsing liquid is supplied from the discharge nozzle 16
- the hydrofluoric acid stored in the processing tank 14 overflows into the outer tank 15, and the processing liquid in the processing tank 14 is eventually replaced with the rinsing liquid from the hydrofluoric acid (step). S13).
- the substrate W is immersed in the rinsing liquid, and the rinsing process in which hydrofluoric acid is washed away from the surface of the substrate W proceeds.
- the rinsing liquid valve 25 is closed, the dopant liquid valve 27 is opened, and the dopant liquid is discharged and supplied from the discharge nozzle 16 into the processing tank 14.
- allylboronic acid pinacol ester is supplied as a dopant liquid.
- the dopant liquid is supplied from the discharge nozzle 16, the rinse liquid stored in the treatment tank 14 overflows to the outer tank 15, and the treatment liquid in the treatment tank 14 is eventually replaced with the dopant liquid from the rinse liquid ( Step S14).
- the substrate W is immersed in the dopant liquid stored in the processing tank 14.
- a thin film containing the dopant is formed on the surface. That is, a large number of dangling bonds (dangling bonds) exist at the ends of the silicon exposed on the surface of the substrate W by removing the natural oxide film 101.
- dangling bonds dangling bonds
- the dopant liquid comes into contact with the surface of the substrate in such a state, molecules containing the dopant are bonded to the dangling bonds of silicon. Note that no new molecule is bonded to the molecule bonded to the silicon dangling bond. Therefore, as shown in FIG. 4C, a monomolecular thin film containing a dopant is formed on the surface of the substrate W (step S15).
- the plurality of substrates W are collectively lifted from the processing tank 14 by the lifter 30, and are lifted to a lifting position above the processing tank 14 and dried. Thereafter, the upper portion 11 is opened, and the plurality of substrates W are further raised from the pulling position by the lifter 30 and transferred to the transfer robot. In this way, a series of thin film forming processes are performed.
- a silicon dioxide cap film is then formed on the thin film on the substrate W on which the monomolecular thin film containing the dopant is formed, and then heat treatment is performed by light irradiation from a halogen lamp or a flash lamp. . By this heat treatment, the dopant of the thin film diffuses into the silicon surface layer of the substrate W, and impurities are introduced into a very shallow region.
- an oxide film removing process for removing the natural oxide film 101 with hydrofluoric acid, a rinsing process for rinsing hydrofluoric acid with a rinsing liquid, and a thin film forming process for forming a thin film containing a dopant with the dopant liquid are continuously performed. And running. Specifically, after removing the natural oxide film 101 with hydrofluoric acid, the rinsing liquid is replaced with a rinsing liquid, and a rinsing process is performed. Subsequently, the rinsing liquid is replaced with a dopant liquid, and a thin film forming process is performed. Yes.
- the dopant liquid comes into contact with the surface of the substrate W from which the natural oxide film 101 is removed and silicon is exposed without contact with moisture. For this reason, the dangling bonds of silicon exposed on the surface of the substrate W are not hydrogen-terminated, and the dopant comes into contact with the surface. Accordingly, the molecule containing the dopant is immediately bonded to the dangling bonds of silicon without causing the process of replacing the hydrogen termination with the dopant by the dopant liquid. As a result, the time required to replace the stable hydrogen termination is reduced, and a thin film containing a dopant can be formed in a short time.
- the time required for the thin film forming process for forming the thin film containing the dopant is about several tens of seconds, which is significantly higher than the technique disclosed in Non-Patent Document 1 (2.5 hours). It will be a short time. Further, when the dopant liquid is brought into contact with the surface of the substrate W in which the dangling bonds of silicon are not hydrogen-terminated, a thin film containing the dopant can be formed uniformly.
- the oxide film removing process, the rinsing process, and the thin film forming process are continuously performed.
- the oxide film removing process and the thin film forming process are performed in parallel. It may be performed simultaneously.
- the hydrofluoric acid valve 23 and the dopant liquid valve 27 are opened in a state where the plurality of substrates W are held at the immersion position in the processing tank 14, and the hydrofluoric acid and the dopant liquid are mixed in the processing tank 14. Supply and store liquid.
- the substrate W is immersed in a mixed liquid of hydrofluoric acid and a dopant liquid.
- a mixed liquid of hydrofluoric acid and a dopant liquid By immersing the substrate W in the mixed solution, the removal of the natural oxide film 101 by hydrofluoric acid and the thin film formation by the dopant solution proceed in parallel, and the dopant is applied to the surface of the substrate W while removing the natural oxide film 101.
- a thin film containing the same is formed. Even if it does in this way, since the silicon dangling bond on the surface of the substrate W is not hydrogen-terminated, the thin film containing the dopant is formed, so that the thin film containing the dopant can be formed in a short time. Further, since the removal of the natural oxide film 101 and the formation of the thin film containing the dopant proceed simultaneously, the time required for the entire process can be shortened. In this case, the rinsing liquid is not supplied.
- the oxide film removing step and the thin film forming step may be partially overlapped. That is, the thin film forming process is started in the middle of the oxide film removing process. Specifically, in a state where the plurality of substrates W are held at the immersion position in the processing tank 14, the hydrofluoric acid valve 23 is opened to store the hydrofluoric acid in the processing tank 14 to remove the natural oxide film 101. To advance. Then, before the oxide film removing step is completed, the dopant liquid valve 27 is opened while the hydrofluoric acid valve 23 is kept open. As a result, the dopant liquid is mixed into the hydrofluoric acid in the treatment tank 14, and a thin film containing the dopant is formed on the surface of the substrate W. Even if it does in this way, since the silicon dangling bond on the surface of the substrate W is not hydrogen-terminated, the thin film containing the dopant is formed, so that the thin film containing the dopant can be formed in a short time.
- the dopant liquid is not limited to allylboronic acid pinacol ester containing boron, and an appropriate one can be selected according to the type of dopant to be introduced (for example, phosphorus (P) or arsenic (As)). .
- FIG. 5 is a longitudinal sectional view of the substrate processing apparatus 5 of the second embodiment.
- the substrate processing apparatus 5 of the second embodiment is a single-wafer type apparatus that surface-treats the substrates W one by one.
- the substrate processing apparatus 5 performs the oxide film removal process with hydrofluoric acid on the plurality of substrates W, and then rinses the hydrofluoric acid from the surface of the substrate W with the rinse liquid, and then removes the dopant.
- a thin film of a monomolecular layer is formed on the surface of the substrate W by the chemical solution that is contained.
- the substrate processing apparatus 5 mainly includes a chamber 50, a substrate holding unit 61, a substrate rotating mechanism 60, a processing liquid supply mechanism 70, a gas supply mechanism 80, a suction mechanism 85, a heating unit 90, and a control unit 99. And comprising.
- the chamber 50 includes a substantially disc-shaped chamber bottom 51, a substantially cylindrical chamber side wall 52 fixed to the outer periphery of the chamber bottom 51, and a substantially disc-shaped chamber lid that closes the upper opening of the chamber side wall 52.
- the chamber lid 53 can be moved in the vertical direction by a drive mechanism (not shown).
- the substrate W 53 is moved upward and the substrate W is carried into and out of the chamber 50 while the upper opening of the chamber side wall 52 is opened. Further, when the chamber lid 53 closes the upper opening of the chamber side wall 52, a processing space 55 that is a sealed space is formed inside the chamber 50.
- the chamber bottom 51 and the chamber lid 53 are made of quartz and transmit light.
- An upper processing liquid pipe 56 is provided vertically through the central portion of the chamber lid 53, and a hollow cylindrical gas pipe 57 is provided around the upper processing liquid pipe 56.
- a lower processing liquid pipe 58 is provided vertically through the center of the chamber bottom 51.
- a plurality of suction pipes 59 are provided at equal intervals in the circumferential direction on the outer periphery of the chamber bottom 51.
- the substrate rotation mechanism 60 is a so-called hollow motor, and is a stator 62 disposed in the circumferential direction inside the chamber side wall 52, and a substantially annular rotor disposed inside the stator 62 in the processing space 55 of the chamber 50. 63.
- the rotor 63 is supported in a non-contact manner by the stator 62 and the chamber side wall 52 by a magnetic force acting between the stator 62 and rotates about an axis along the vertical direction.
- the substrate holding unit 61 is a substantially annular plate-like member fixed to the inner peripheral surface of the rotor 63 of the substrate rotation mechanism 60 and is accommodated in the processing space 55 of the chamber 50 together with the rotor 63.
- the substrate W is held on the substrate holding unit 61 by being placed on the substrate holding unit 61 with the surface facing upward. That is, the substrate holding unit 61 holds the substrate W by supporting the lower surface of the peripheral edge of the substrate W.
- maintenance part 61 may be a some convex part which protrudes toward the radial inside from the internal peripheral surface of the rotor 63, for example.
- the substrate rotating mechanism 60 rotates the rotor 63, the substrate holding unit 61, and the substrate W held by the substrate holding unit 61 around the center axis passing through the center of the substrate W along the vertical direction.
- the processing liquid supply mechanism 70 is a mechanism for supplying various processing liquids to the processing space 55.
- the front end side of the supply pipe 71 of the processing liquid supply mechanism 70 is branched into two, one connected to the upper processing liquid pipe 56 and the other connected to the lower processing liquid pipe 58.
- the base end side of the supply pipe 71 is branched into three and connected to a hydrofluoric acid supply source 72, a rinse liquid supply source 74, and a dopant liquid supply source 76, respectively.
- a hydrofluoric acid valve 73 is provided for a pipe connected to the hydrofluoric acid supply source 72
- a rinse liquid valve is provided for a pipe connected to the rinse liquid supply source 74.
- the pipe 75 connected to the dopant liquid supply source 76 is provided with a dopant liquid valve 77.
- hydrofluoric acid is supplied from the hydrofluoric acid supply source 72 to the upper processing liquid pipe 56 and the lower processing liquid pipe 58. Then, hydrofluoric acid is supplied from the upper processing liquid pipe 56 toward the center of the upper surface of the substrate W held by the substrate holding unit 61. Hydrofluoric acid is supplied from the lower processing liquid pipe 58 toward the center of the lower surface of the substrate W held by the substrate holding unit 61.
- concentration of hydrofluoric acid supplied by the hydrofluoric acid supply source 72 is appropriate.
- the rinse liquid is supplied from the rinse liquid supply source 74 to the upper process liquid pipe 56 and the lower process liquid pipe 58.
- the rinsing liquid is supplied from the upper processing liquid pipe 56 toward the center of the upper surface of the substrate W held by the substrate holding part 61, and the substrate held by the substrate holding part 61 is supplied from the lower processing liquid pipe 58.
- a rinsing liquid is supplied toward the center of the lower surface of W.
- Alcohols are used as the rinsing liquid, and IPA is also used in the second embodiment.
- the alcohol used as the rinsing liquid is not limited to IPA, and may be ethanol.
- the dopant liquid valve 77 when the dopant liquid valve 77 is opened, the dopant liquid is fed from the dopant liquid supply source 76 to the upper processing liquid pipe 56 and the lower processing liquid pipe 58.
- the dopant liquid is supplied from the upper processing liquid pipe 56 toward the center of the upper surface of the substrate W held by the substrate holding part 61, and the substrate held by the substrate holding part 61 is supplied from the lower processing liquid pipe 58.
- the dopant liquid is supplied toward the center of the lower surface of W.
- the dopant liquid is a chemical liquid containing a dopant, and has a property of forming a monolayer thin film containing the dopant on the surface by contacting the surface of the silicon substrate W.
- allylboronic acid pinacol ester containing boron is used as the dopant liquid.
- any one of the hydrofluoric acid valve 73, the rinsing liquid valve 75, and the dopant liquid valve 77 may be opened selectively, or two or more may be opened simultaneously.
- the hydrofluoric acid valve 73 and the dopant liquid valve 77 are opened simultaneously, the mixed liquid of hydrofluoric acid and the dopant liquid is supplied to the processing space 55.
- the gas supply mechanism 80 includes a pipe 81, a gas supply source 82, and a gas valve 83.
- the distal end of the pipe 81 is connected to a gas pipe 57 provided in the chamber lid portion 53.
- nitrogen gas is supplied from the gas supply source 82 to the processing space 55 in the chamber 50.
- the suction mechanism 85 includes a pipe 86, a suction unit 87, and a suction valve 88.
- the distal end of the pipe 86 is branched into a plurality of parts and connected to a plurality of suction pipes 59 provided on the outer periphery of the chamber bottom 51.
- the suction valve 88 By opening the suction valve 88 while operating the suction portion 87, the atmosphere of the processing space 55 in the chamber 50 is exhausted to the outside of the apparatus.
- the suction space 87 can make the processing space 55 a reduced-pressure atmosphere less than atmospheric pressure.
- the suction mechanism 85 also discharges the processing liquid supplied into the chamber 50 to the outside of the apparatus. That is, the suction mechanism 85 discharges both gas and liquid from the processing space 55.
- the heating unit 90 includes lamps 91 disposed above and below the chamber 50.
- the lamp 91 heats the substrate W by irradiating light toward the substrate W through the quartz chamber bottom 51 and the chamber lid 53.
- the control unit 99 includes the various operation mechanisms (the substrate rotation mechanism 60, the hydrofluoric acid valve 73, the rinse liquid valve 75, the dopant liquid valve 77, the gas valve 83, the suction unit 87, and the suction valve 88 provided in the substrate processing apparatus 5. , Lamp 91, etc.).
- the configuration of the control unit 99 as hardware is the same as that of a general computer. That is, the control unit 99 stores a CPU that performs various arithmetic processes, a ROM that is a read-only memory that stores basic programs, a RAM that is a readable and writable memory that stores various information, control software, data, and the like. It is configured with a magnetic disk.
- the processing in the substrate processing apparatus 5 proceeds when the CPU of the control unit 99 executes a predetermined processing program.
- FIG. 6 is a flowchart showing a processing procedure in the substrate processing apparatus 5. The processing procedure shown below proceeds by the control unit 99 controlling each operation mechanism of the substrate processing apparatus 5.
- the chamber lid 53 moves upward, the upper opening of the chamber side wall 52 is opened, and the substrate W is loaded into the chamber 50 by a transfer robot (not shown).
- a natural oxide film 101 of silicon dioxide is formed on the surface of the silicon substrate W (see FIG. 4A).
- the surface of the substrate W is a main surface on which a device pattern is formed, and the back surface is a main surface on the opposite side.
- the loaded substrate W is held by the substrate holding unit 61 with the surface facing upward.
- the chamber lid part 53 obstruct
- the gas valve 83 is opened, and nitrogen gas is supplied from the gas pipe 57 to the processing space 55.
- the suction valve 88 is opened while the suction portion 87 is operated, and the processing space 55 is exhausted, so that the processing space 55 in the chamber 50 is replaced with a nitrogen atmosphere. Subsequent surface treatment of the substrate W proceeds in a nitrogen atmosphere.
- the processing space 55 is replaced with a nitrogen atmosphere, and the rotation of the substrate W is started by the substrate rotation mechanism 60 (step S21).
- the substrate W is rotated in a substantially horizontal plane with the center axis passing through the center in the vertical direction as the center of rotation.
- the hydrofluoric acid valve 73 is opened, and hydrofluoric acid is supplied from the upper processing liquid pipe 56 to the vicinity of the center of the upper surface of the substrate W and from the lower processing liquid pipe 58 to the vicinity of the center of the lower surface of the substrate W (step S22).
- the hydrofluoric acid supplied to the vicinity of the center of the upper and lower surfaces of the substrate W spreads to the peripheral edge of the substrate W due to the centrifugal force accompanying the rotation of the substrate W. Thereby, the entire surface of the substrate W is covered with hydrofluoric acid.
- the natural oxide film 101 of silicon dioxide formed on the surface of the substrate W is removed by etching (step S23). As a result, silicon is exposed on the surface of the substrate W (see FIG. 4B).
- the processing liquid scattered from the peripheral edge of the substrate W is sucked by the suction mechanism 85 and discharged outside the apparatus.
- the hydrofluoric acid valve 73 is closed and the supply of hydrofluoric acid is stopped.
- the rinsing liquid valve 75 is opened, and the rinsing liquid is supplied from the upper processing liquid pipe 56 to the vicinity of the center of the upper surface of the substrate W and from the lower processing liquid pipe 58 to the vicinity of the center of the lower surface of the substrate W (step S24).
- IPA is supplied as the rinse liquid.
- the rinse liquid supplied to the vicinity of the center of the upper surface and the lower surface of the substrate W spreads to the peripheral edge of the substrate W due to the centrifugal force accompanying the rotation of the substrate W. Thereby, a rinsing process in which hydrofluoric acid is washed away from the surface of the substrate W proceeds.
- the surface of the substrate W is not covered with the liquid and the atmosphere of the processing space 55 from when the supply of hydrofluoric acid is stopped until the rinsing process is started after the oxide film removing process is completed. Will be exposed. However, since the processing space 55 has a nitrogen atmosphere and oxygen and hydrogen do not exist, the surface of the substrate W from which silicon is exposed is prevented from being oxidized again or terminated with hydrogen.
- the rinsing liquid valve 75 is closed and the supply of the rinsing liquid is stopped. Subsequently, the dopant liquid valve 77 is opened, and the dopant liquid is supplied from the upper processing liquid pipe 56 to the vicinity of the center of the upper surface of the substrate W and from the lower processing liquid pipe 58 to the vicinity of the center of the lower surface of the substrate W (step S25). Also in the second embodiment, allylboronic acid pinacol ester is supplied as a dopant solution.
- the dopant liquid supplied to the vicinity of the center of the upper surface and the lower surface of the substrate W spreads to the peripheral portion of the substrate W due to the centrifugal force accompanying the rotation of the substrate W. As a result, the entire surface of the substrate W is covered with the dopant liquid. Note that the surface of the substrate W is oxidized or hydrogen-terminated since the processing space 55 is in a nitrogen atmosphere even after the supply of the rinsing liquid is stopped until the supply of the dopant liquid is started. That is prevented.
- a thin film containing the dopant is formed on the surface. Similar to the first embodiment, there are many dangling bonds at the ends of the silicon exposed on the surface of the substrate W by removing the natural oxide film 101, and the dopant liquid is in contact with the surface of the substrate W. As a result, a monolayer thin film containing a dopant is formed on the surface (step S26).
- step S27 After the dopant thin film is formed on the surface of the substrate W, the rotation of the substrate W by the substrate rotation mechanism 60 is stopped (step S27). Thereafter, the chamber lid 53 moves upward, the upper opening of the chamber side wall 52 is opened, and the processed substrate W is unloaded from the chamber 50 by a transfer robot (not shown). In this way, a series of thin film forming processes are performed.
- the oxide film removing step of removing the natural oxide film 101 with hydrofluoric acid, the rinsing step of rinsing off the hydrofluoric acid with a rinsing liquid, and the thin film forming step of forming a thin film containing a dopant with the dopant liquid are performed.
- Running in an atmosphere that is, running in a non-atmospheric atmosphere in which oxygen and hydrogen are not present. For this reason, the dangling bonds of silicon exposed on the surface of the substrate W are not oxidized or hydrogen-terminated, and the dopant comes into contact with the surface.
- the molecule containing the dopant is immediately bonded to the dangling bonds of silicon without causing the process of replacing the hydrogen termination with the dopant by the dopant liquid.
- the time required to replace the hydrogen termination is reduced, and a thin film containing a dopant can be formed in a short time.
- the time required for the thin film forming process for forming the thin film containing the dopant is about several tens of seconds.
- the oxide film removing step, the rinsing step, and the thin film forming step are performed in a nitrogen atmosphere, but this may be performed in a reduced pressure atmosphere.
- the suction valve 88 is opened while the gas valve 83 is closed, and the processing space 55 in the chamber 50 is made less than atmospheric pressure by exhausting by the suction unit 87.
- the reduced pressure atmosphere is performed after the substrate W is loaded and the inside of the chamber 50 is sealed.
- steps S21 to S27 similar to those in the second embodiment are performed in a reduced pressure atmosphere. Even if it does in this way, a series of oxide film removal processes, a rinse process, and a thin film formation process are performed in the atmosphere which does not contain hydrogen. For this reason, the thin film containing the dopant is formed without the silicon dangling bonds on the surface of the substrate W being terminated with hydrogen, and the thin film containing the dopant can be formed in a short time. That is, the series of oxide film removal step, rinse step, and thin film formation step may be performed in a non-air atmosphere such as a nitrogen atmosphere or a reduced pressure atmosphere.
- a non-air atmosphere such as a nitrogen atmosphere or a reduced pressure atmosphere.
- the oxide film removing step, the rinsing step, and the thin film forming step may be slightly overlapped and executed continuously.
- the rinsing liquid valve 75 is opened before the hydrofluoric acid valve 73 is closed, and the fluoric acid covering the surface of the substrate W is replaced with the rinsing liquid.
- the dopant liquid valve 77 is opened before the rinse liquid valve 75 is closed, and the rinse liquid covering the surface of the substrate W is replaced with the dopant liquid. In this way, the surface of the substrate W is always covered with the liquid during a series of processing steps, and the surface of the substrate W is not exposed to the atmosphere of the processing space 55.
- the processing space 55 is not in a non-atmosphere atmosphere, the dangling bonds of silicon exposed on the surface of the substrate W are not hydrogen-terminated and the dopant comes into contact with the surface as in the first embodiment.
- a thin film containing a dopant can be formed in a short time.
- FIG. 7 is a timing chart showing an example in which the oxide film removing step and the thin film forming step are overlapped.
- the oxide film removing step and the thin film forming step are partially overlapped. That is, the thin film forming process is started in the middle of the oxide film removing process.
- the hydrofluoric acid valve 73 is opened, and supply of hydrofluoric acid to the surface of the rotating substrate W is started.
- the dopant liquid valve 77 is opened before the hydrofluoric acid valve 73 is closed, and the dopant liquid is started while the hydrofluoric acid is being supplied. Supply.
- the dopant liquid is mixed into the hydrofluoric acid covering the surface of the substrate, and the dopant liquid immediately contacts the surface of the substrate W from which the natural oxide film 101 has been removed. Even if it does in this way, since the silicon dangling bond on the surface of the substrate W is not hydrogen-terminated, the thin film containing the dopant is formed, so that the thin film containing the dopant can be formed in a short time.
- the oxide film removing step and the thin film forming step are completely overlapped. That is, the oxide film removing step and the thin film forming step are simultaneously performed in parallel. Specifically, the hydrofluoric acid valve 73 and the dopant liquid valve 77 are simultaneously opened, and supply of a mixed liquid of hydrofluoric acid and dopant liquid to the surface of the rotating substrate W is started. As a result, the entire surface of the substrate W is covered with the mixed liquid of hydrofluoric acid and the dopant liquid.
- the removal of the natural oxide film 101 with hydrofluoric acid and the thin film formation with the dopant solution proceed in parallel, and a thin film containing the dopant is formed on the surface of the substrate W while removing the natural oxide film 101.
- the silicon dangling bond on the surface of the substrate W is not hydrogen-terminated, the thin film containing the dopant is formed, so that the thin film containing the dopant can be formed in a short time.
- the rinsing process is omitted and the removal of the natural oxide film 101 and the formation of the thin film containing the dopant proceed simultaneously, the time required for the entire process can be shortened.
- the dopant liquid is not limited to allylboronic acid pinacol ester containing boron, and may be appropriately selected according to the type of dopant to be introduced (for example, phosphorus (P) or arsenic (As)). Can choose.
- Substrate processing apparatus 10 1, 5 Substrate processing apparatus 10, 50 Chamber 14 Processing tank 16 Discharge nozzle 20, 70 Processing liquid supply mechanism 22, 72 Hydrofluoric acid supply source 23, 73 Hydrofluoric acid valve 24, 74 Rinse liquid supply source 25, 75 Rinse liquid valve 26 , 76 Dopant solution supply source 27, 77 Dopant solution valve 30 Lifter 35, 80 Gas supply mechanism 40 Exhaust mechanism 49, 99 Control unit 55 Processing space 56 Upper process solution piping 58 Lower process solution piping 60 Substrate rotation mechanism 61 Substrate holding unit 85 Suction mechanism
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Abstract
Description
<1-1.装置全体構成>
図1は、第1実施形態の基板処理装置1を、基板Wと平行な平面で切断した縦断面図である。図2は、図1の基板処理装置1をA-A位置で切断した縦断面図である。第1実施形態の基板処理装置1は、複数枚の基板Wに対して一括して表面処理を行うバッチ式の装置である。
次に、上記の構成を有する第1実施形態の基板処理装置1における基板処理動作について説明する。図3は、基板処理装置1における処理手順を示すフローチャートである。また、図4は、基板処理にともなう、基板Wの表面状態の変化を示す図である。以下に示す処理手順は、制御部49が基板処理装置1の各動作機構を制御することによって進行される。
以上、本発明の第1の実施の形態について説明したが、この発明はその趣旨を逸脱しない限りにおいて上述したもの以外に種々の変更を行うことが可能である。例えば、第1実施形態においては、酸化膜除去工程、リンス工程、および、薄膜形成工程、を連続して実行していたが、これらのうちの酸化膜除去工程と薄膜形成工程とを並行して同時に行うようにしても良い。具体的には、複数の基板Wを処理槽14内の浸漬位置に保持した状態にて、フッ酸バルブ23およびドーパント液バルブ27を開放し、処理槽14内にフッ酸とドーパント液との混合液を供給して貯留する。基板Wはフッ酸とドーパント液との混合液中に浸漬されることとなる。基板Wが混合液中に浸漬されることにより、フッ酸による自然酸化膜101の除去とドーパント液による薄膜形成とが並行して進行し、自然酸化膜101を除去しつつ基板Wの表面にドーパントを含む薄膜を形成することとなる。このようにしても、基板W表面のシリコン未結合手が水素終端されることなく、ドーパントを含む薄膜が形成されることとなるため、ドーパントを含む薄膜を短時間にて形成することができる。また、自然酸化膜101の除去とドーパントを含む薄膜の形成とが同時に進行するため、処理全体に要する時間も短時間とすることができる。なお、この場合、リンス液の供給は行わない。
<2-1.装置全体構成>
次に、本発明の第2実施形態について説明する。図5は、第2実施形態の基板処理装置5の縦断面図である。第2実施形態の基板処理装置5は、基板Wを1枚ずつ表面処理する枚葉式の装置である。
次に、上記の構成を有する第2実施形態の基板処理装置5における基板処理動作について説明する。図6は、基板処理装置5における処理手順を示すフローチャートである。以下に示す処理手順は、制御部99が基板処理装置5の各動作機構を制御することによって進行される。
以上、本発明の第2の実施の形態について説明したが、この発明はその趣旨を逸脱しない限りにおいて上述したもの以外に種々の変更を行うことが可能である。例えば、第2実施形態においては、酸化膜除去工程、リンス工程、および、薄膜形成工程、を窒素雰囲気にて実行していたが、これを減圧雰囲気下にて行うようにしても良い。具体的には、基板Wが搬入されてチャンバー50内が密閉された後、ガスバルブ83を閉止したまま吸引バルブ88を開放し、吸引部87による排気によってチャンバー50内の処理空間55を大気圧未満の減圧雰囲気とする。そして、減圧雰囲気下にて上記第2実施形態と同様のステップS21~ステップS27の処理を行う。このようにしても、一連の酸化膜除去工程、リンス工程、および、薄膜形成工程が水素を含まない雰囲気にて実行される。このため、基板W表面のシリコン未結合手が水素終端されることなく、ドーパントを含む薄膜が形成されることとなり、ドーパントを含む薄膜を短時間にて形成することができる。すなわち、一連の酸化膜除去工程、リンス工程、および、薄膜形成工程は、窒素雰囲気または減圧雰囲気などの非大気雰囲気にて実行すれば良い。
10,50 チャンバー
14 処理槽
16 吐出ノズル
20,70 処理液供給機構
22,72 フッ酸供給源
23,73 フッ酸バルブ
24,74 リンス液供給源
25,75 リンス液バルブ
26,76 ドーパント液供給源
27,77 ドーパント液バルブ
30 リフタ
35,80 ガス供給機構
40 排気機構
49,99 制御部
55 処理空間
56 上部処理液配管
58 下部処理液配管
60 基板回転機構
61 基板保持部
85 吸引機構
Claims (12)
- 基板の表面にドーパントを含む薄膜を形成する基板処理方法であって、
表面から酸化膜が除去された基板に水素終端を実行することなく、当該基板の表面にドーパント液を供給してドーパントを含む薄膜を形成する基板処理方法。 - 請求項1記載の基板処理方法において、
基板の表面にフッ酸を供給して当該表面に形成された酸化膜を除去する酸化膜除去工程と、
前記酸化膜除去工程の後、前記表面にリンス液を供給してフッ酸を洗い流すリンス工程と、
前記リンス工程の後、前記表面にドーパント液を供給して薄膜を形成する薄膜形成工程と、
を備える基板処理方法。 - 請求項2記載の基板処理方法において、
前記酸化膜除去工程、前記リンス工程、および、前記薄膜形成工程を連続して実行する基板処理方法。 - 請求項2記載の基板処理方法において、
前記酸化膜除去工程、前記リンス工程、および、前記薄膜形成工程を非大気雰囲気にて実行する基板処理方法。 - 請求項1記載の基板処理方法において、
基板の表面にフッ酸とドーパント液との混合液を供給し、前記表面に形成された酸化膜を除去しつつ前記表面にドーパントを含む薄膜を形成する基板処理方法。 - 請求項1記載の基板処理方法において、
基板の表面にフッ酸を供給して当該表面に形成された酸化膜を除去する酸化膜除去工程と、
前記表面にドーパント液を供給して薄膜を形成する薄膜形成工程と、
を備え、
前記酸化膜除去工程の途中から前記薄膜形成工程を開始する基板処理方法。 - 請求項1から請求項6のいずれかに記載の基板処理方法において、
ドーパント液によって基板の表面に形成される薄膜は単分子層である基板処理方法。 - 基板の表面にドーパントを含む薄膜を形成する基板処理装置であって、
基板を収容するチャンバーと、
前記チャンバー内にて基板を保持する保持手段と、
前記保持手段に保持された基板の表面にフッ酸を供給して当該表面に形成された酸化膜を除去するフッ酸供給手段と、
前記基板の表面にリンス液を供給してフッ酸を洗い流すリンス液供給手段と、
前記基板の表面にドーパント液を供給して薄膜を形成するドーパント液供給手段と、
前記表面へのフッ酸供給、リンス液供給、および、ドーパント液供給を連続して行うように前記フッ酸供給手段、前記リンス液供給手段および前記ドーパント液供給手段を制御する制御手段と、
を備える基板処理装置。 - 基板の表面にドーパントを含む薄膜を形成する基板処理装置であって、
基板を収容するチャンバーと、
前記チャンバー内にて基板を保持する保持手段と、
前記保持手段に保持された基板の表面にフッ酸を供給して当該表面に形成された酸化膜を除去するフッ酸供給手段と、
前記基板の表面にドーパント液を供給して薄膜を形成するドーパント液供給手段と、
前記表面にフッ酸を供給している途中からドーパント液の供給を開始するように前記フッ酸供給手段および前記ドーパント液供給手段を制御する制御手段と、
を備える基板処理装置。 - 基板の表面にドーパントを含む薄膜を形成する基板処理装置であって、
処理液を貯留可能な処理槽と、
前記処理槽に貯留された処理液中に浸漬する浸漬位置に基板を保持する保持手段と、
前記処理槽にフッ酸を供給するフッ酸供給手段と、
前記処理槽にリンス液を供給するリンス液供給手段と、
前記処理槽にドーパント液を供給するドーパント液供給手段と、
前記浸漬位置に基板を保持した状態にて、前記処理槽にフッ酸を供給してフッ酸を貯留した後、前記処理槽にリンス液を供給してフッ酸をリンス液に置換し、その後前記処理槽にドーパント液を供給してリンス液をドーパント液に置換するように、前記フッ酸供給手段、前記リンス液供給手段および前記ドーパント液供給手段を制御する制御手段と、
を備える基板処理装置。 - 基板の表面にドーパントを含む薄膜を形成する基板処理装置であって、
処理液を貯留可能な処理槽と、
前記処理槽に貯留された処理液中に浸漬する浸漬位置に基板を保持する保持手段と、
前記処理槽にフッ酸を供給するフッ酸供給手段と、
前記処理槽にドーパント液を供給するドーパント液供給手段と、
前記浸漬位置に基板を保持した状態にて、前記処理槽にフッ酸とドーパント液との混合液供給して当該混合液を貯留するように、前記フッ酸供給手段および前記ドーパント液供給手段を制御する制御手段と、
を備える基板処理装置。 - 請求項8から請求項11のいずれかに記載の基板処理装置において、
ドーパント液によって基板の表面に形成される薄膜は単分子層である基板処理装置。
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