US20190019670A1 - Apparatus and method for removal of oxide and carbon from semiconductor films in a single processing chamber - Google Patents

Apparatus and method for removal of oxide and carbon from semiconductor films in a single processing chamber Download PDF

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Publication number
US20190019670A1
US20190019670A1 US16/000,109 US201816000109A US2019019670A1 US 20190019670 A1 US20190019670 A1 US 20190019670A1 US 201816000109 A US201816000109 A US 201816000109A US 2019019670 A1 US2019019670 A1 US 2019019670A1
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gas
oxide
substrate
remote plasma
flowing
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US16/000,109
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Xing Lin
Peipei Gao
Fei Wang
John Tolle
Bubesh Babu JOTHEESWARAN
Vish Ramanathan
Eric Hill
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ASM IP Holding BV
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ASM IP Holding BV
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Priority to US16/000,109 priority Critical patent/US20190019670A1/en
Publication of US20190019670A1 publication Critical patent/US20190019670A1/en
Assigned to ASM IP HOLDING B.V. reassignment ASM IP HOLDING B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JOTHEESWARAN, Bubesh Babu, TOLLE, JOHN, Gao, Peipei, HILL, ERIC, LIN, Xing, Ramanathan, Vish, WANG, FEI
Priority to US17/875,907 priority patent/US20220367175A1/en
Abandoned legal-status Critical Current

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    • 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
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02046—Dry cleaning only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B5/00—Cleaning by methods involving the use of air flow or gas flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32357—Generation remote from the workpiece, e.g. down-stream
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3244—Gas supply means
    • H01J37/32449—Gas control, e.g. control of the gas flow
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32715—Workpiece holder
    • 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
    • H01L21/31—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
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H01L21/31138—Etching organic layers by chemical means by dry-etching
    • 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
    • H01L21/67017—Apparatus for fluid treatment

Definitions

  • the present disclosure generally relates to an apparatus and a method for manufacturing electronic devices. More particularly, the disclosure relates to removal of oxide and carbon within semiconductor films formed in a processing chamber.
  • a clean surface of a wafer or substrate Prior to the fabrication of semiconductor device, a clean surface of a wafer or substrate is desired. Contaminates on the substrate may adversely affect mechanical and electrical properties of the semiconductor devices formed. It is desired that these contaminates be removed before particular films are deposited onto the substrate.
  • Contaminants that exist on a silicon or silicon germanium substrate may include carbon-based contaminants, such as carbonaceous contaminants and hydrocarbon contaminates. Other contaminants may include oxygen-based contaminants, such as native oxides, for example. It may be imperative to remove these contaminants before epitaxial processes can take place.
  • Prior approaches to contaminant removal focus on removing one of the contaminants, either carbon-based or oxygen-based, but not both. This may be in part due to equipment limitations of the prior approaches. As a result, a system and method to remove both carbon-based and oxygen-based contaminants is desired.
  • FIG. 1 is a cross-sectional illustration of a system in accordance with at least one embodiment of the invention.
  • FIG. 2 is a cross-sectional illustration of a system in accordance with at least one embodiment of the invention.
  • FIGS. 3A, 3B and 3C are flowcharts of methods in accordance with at least one embodiment of the invention.
  • FIG. 4 is a flowchart of a step in accordance with at least one embodiment of the invention.
  • FIG. 5 is a flowchart of a step in accordance with at least one embodiment of the invention.
  • FIG. 6 is a flowchart of a step in accordance with at least one embodiment of the invention.
  • Embodiments of the invention are directed to a system with a single process chamber having a capability to remove both carbon-based contaminants and oxygen-based contaminants.
  • the embodiments have several advantages over prior approaches including: (1) incorporation of at least one remote plasma unit (RPU) with the ability to generate both hydrogen radicals and fluorine radicals; and (2) compatibility of the process chamber with both hydrogen radicals and fluorine radicals.
  • RPU remote plasma unit
  • Embodiments of the invention may be used to clean semiconductor substrates made of at least one of the following materials: silicon; silicon germanium; or germanium, for example. In one embodiment, the percentage of germanium in silicon germanium may vary from 10% to 90%. Also, embodiments of the invention may be used to etch carbon layers, such as an advanced patterning film (APF); photoresists; or other carbon contaminations including CHF x , SiC, or SiOC. In addition, embodiments of the invention may be used to clean a surface of dielectric materials, such as silicon oxide, silicon nitride, silicon oxynitride, fluorinated silicon oxide, silicon carboxide, and silicon carboxynitride. Furthermore, embodiments of the invention may be applied to patterned wafer surfaces.
  • APF advanced patterning film
  • FIG. 1 illustrates a system 100 in accordance with at least one embodiment of the invention.
  • the system 100 may comprise a reaction chamber 110 , a susceptor 120 , a showerhead 130 , a remote plasma unit 140 , and a transport path 145 between the remote plasma unit 140 and the reaction chamber 110 .
  • a substrate 150 is placed on the susceptor 120 for processing.
  • the reaction chamber 110 defines a space in which the substrate 150 is processed.
  • the reaction chamber 110 , the susceptor 120 , the showerhead 130 , and the transport path 145 may be coated with materials or bulk ceramic material in order to allow for compatibility with different radicals.
  • the materials for coating may include at least one of: anodized aluminum oxide (Al 2 O 3 ); atomic layer deposition (ALD)-formed aluminum oxide; plasma sprayed Al 2 O 3 ; bare aluminum parts with native aluminum oxide, yttrium oxide (Y 2 O 3 ); yttrium oxide stabilized zirconium oxide (YSZ); zirconium oxide (ZrO 2 ); lanthanum zirconium oxide (LZO); yttrium aluminum garnet (YAG); yttrium oxyfluoride (YOF); combination of the above materials; or the above substrate doped with other glass phase materials.
  • Al 2 O 3 anodized aluminum oxide
  • ALD atomic layer deposition
  • Al 2 O 3
  • the coating materials can be made with two layers.
  • the first layer may be coated with anodized Al 2 O 3 and the second layer may be coated with ALD-formed Al 2 O 3 .
  • the coating may be amorphous phase, crystalline phase, or mixed.
  • the bulk ceramic material may include: aluminum oxide (Al 2 O 3 ); zirconium oxide (ZrO 2 ); yttrium oxide (Y 2 O 3 ); or yttrium oxide stabilized zirconium oxide (YSZ).
  • the system 100 also may comprise a first gas source 160 , a second gas source 170 , a third gas source 180 , and a fourth gas source 190 , which all may provide gas to the remote plasma unit 140 .
  • the remote plasma unit 140 may comprise a Paragon H* remote plasma unit from MKS Instruments, for example.
  • the third gas source 180 may also be configured to provide gas directly into the reaction chamber 110 without going through the remote plasma unit 140 .
  • the first gas source 160 may comprise a source of a precursor gas that produces fluorine radicals, such as NF 3 , CF 4 , C 2 F 6 , C 4 F 6 , C 4 F 8 , COF 2 , SF 6 , or WF 6 , for example.
  • the second gas source 170 may comprise a source of a gas that produces hydrogen radicals, such as H 2 , NH 3 , or H 2 O, for example.
  • the second gas source 170 may comprise a gas that produces oxygen radicals, such as oxygen or ozone, for example.
  • the third gas source 180 may be a source of NH 3 .
  • the fourth gas source 190 may be a source of an inert gas, such as argon, helium, nitrogen, or neon, for example.
  • the remote plasma unit 140 generates radicals provided from the gas sources.
  • the generated radicals then enter the reaction chamber 110 through the showerhead 130 and then flow onto the substrate 150 .
  • the remote plasma source may include: a toroidal style ICP source or a coil style ICP source driven by different RF frequencies, such as a 400 kHz, 2 MHz, 60 MHz and 2.56 GHz microwave source.
  • FIG. 2 illustrates a system 200 in accordance with at least one embodiment of the invention.
  • the system 200 may comprise a reaction chamber 210 , a susceptor 220 , a showerhead 230 , a first remote plasma unit 240 dedicating for oxide removal with F*, a second remote plasma unit 245 dedicating for carbon removal with H*, a transport path 246 below the first remote plasma unit, and a transport path 247 below the second remote plasma unit.
  • a substrate 250 is placed on the susceptor 220 for processing.
  • the system 200 may also comprise a first gate vale 248 and a second gate valve 249 .
  • the reaction chamber 210 defines a space in which the substrate 250 is processed.
  • the reaction chamber 210 , the susceptor 220 , and the showerhead 230 may be coated with materials or bulk ceramic material in order to allow for compatibility with different radicals, such as: anodized aluminum oxide (Al 2 O 3 ); atomic layer deposition (ALD)-formed aluminum oxide; plasma sprayed Al 2 O 3 ; bare aluminum parts with native aluminum oxide; yttrium oxide (Y 2 O 3 ); yttrium oxide stabilized zirconium oxide (YSZ); zirconium oxide (ZrO 2 ); lanthanum zirconium oxide (LZO); yttrium aluminum garnet (YAG); yttrium oxyfluoride (YOF); combination of the above materials; or the above substrate doped with other glass phase materials.
  • ALD atomic layer deposition
  • the coating materials may be made with two layers.
  • the first layer may be coated with anodized Al 2 O 3 and the second layer may be coated with ALD-formed Al 2 O 3 .
  • the coating may be amorphous phase, crystalline phase, or mixed.
  • the bulk ceramic material may include: aluminum oxide (Al 2 O 3 ); zirconium oxide (ZrO 2 ); yttrium oxide (Y 2 O 3 ); or yttrium oxide-stabilized zirconium oxide (YSZ).
  • materials for the transport path 247 below the second remote plasma unit may also comprise bulk quartz material.
  • the system 200 also may comprise a first gas source 260 , a second gas source 270 , a third gas source 280 , and a fourth gas source 290 , which all may provide gas to the first remote plasma unit 240 and the second remote plasma unit 245 .
  • the first remote plasma unit 240 and the second remote plasma unit 245 may comprise a toroidal style ICP source or a coil style ICP source driven by different RF frequencies, such as a 400 kHz, 2 MHz, 60 MHz and 2.56 GHz microwave source, for example.
  • the third gas source 280 may also be configured to provide gas directly into the reaction chamber 210 without going through the first remote plasma unit 240 or the second remote plasma unit 245 .
  • the first gas source 260 may comprise a source of a precursor gas that produces fluorine radicals, such as NF 3 , CF 4 , C 2 F 6 , C 4 F 6 , C 4 F 8 , COF 2 , SF 6 , or WF 6 , for example.
  • the second gas source 270 may comprise a source of gas that produces hydrogen radicals, such as H 2 , NH 3 , or H 2 O, for example.
  • the second gas source 270 may comprise a gas that produces oxygen radicals, such as oxygen or ozone, for example.
  • the third gas source 280 may be a source of NH 3 .
  • the fourth gas source 290 may be a source of an inert gas, such as argon, helium, nitrogen, or neon, for example.
  • the first remote plasma unit 240 (which may be dedicated for F* radicals) and the second remote plasma unit 245 (which may be dedicated for H* radicals) generate radicals provided from the gas sources.
  • the generated radicals then enter the reaction chamber 210 through the showerhead 230 and then flow onto the substrate 250 .
  • the gate valves 248 and 249 may be located at the outlet of RPU.
  • FIG. 3A illustrates a method in accordance with at least one embodiment of the invention.
  • the method comprises an oxide conversion step 300 , an oxide sublimation step 400 , and a carbon removal step 500 . Any of these steps or any combination of these steps may be repeated as needed.
  • the entire method may be repeated through a repeat cycle 600 .
  • FIG. 3B illustrates a method in accordance with at least one embodiment of the invention.
  • the method comprises a carbon removal step 500 , an oxide conversion step 300 , and an oxide sublimation step 400 . Any of these steps or any combination of these steps may be repeated as needed.
  • the entire method may be repeated through a repeat cycle 600 .
  • the method of FIG. 3B differs from that of FIG. 3A in that the carbon removal step 500 comes before the oxide conversion step 300 .
  • FIG. 3C illustrates a method in accordance with at least one embodiment of the invention.
  • the method comprises a carbon removal step 500 , an oxide conversion step 300 , an oxide sublimation step 400 , and a carbon removal step 500 . Any of these steps or any combination of these steps may be repeated as needed.
  • the entire method may be repeated through a repeat cycle 600 .
  • the method of FIG. 3C differs from that of FIG. 3B in that an additional carbon removal step 500 comes after the oxide sublimation step 400 .
  • the oxide conversion step 300 is illustrated in FIG. 4 .
  • the oxide conversion step 300 may comprises a step 310 of flowing gaseous precursors into a remote plasma unit and a step 320 of flowing generated radicals and an additional precursor onto a substrate.
  • the step 310 may comprise flow of argon, hydrogen, and NF 3 into the remote plasma unit.
  • a flow of argon may range between 0.01 and 20 slm, between 0.1 and 10 slm, or between 1 and 8 slm.
  • a flow of hydrogen may range between 10 sccm and 1500 slm, between 25 and 1200 slm, or between 50 sccm and 1000 slm.
  • a flow of NF 3 may occur for a particular amount of time while the plasma is on in the remote plasma unit, ranging between 0.1 and 120 seconds, between 1 and 100 seconds, or between 5 and 80 seconds.
  • the step 310 may comprise heating the reaction chamber 210 to a temperature between than 5 to 120° C., between than 5 to 80° C., or between than 5 to 60° C.
  • a gas of fluorine radicals is generated in the remote plasma unit.
  • the fluorine radicals leave the remote plasma unit and may combine with an optional additional precursor gas in step 320 onto the substrate disposed in a reaction chamber.
  • the optional additional precursor gas may comprise ammonia flowed at a rate ranging between 10 sccm and 1500 slm, between 25 and 1200 slm, or between 50 sccm and 1000 slm.
  • the step 320 may comprise heating the reaction chamber 210 to a temperature between than 5 to 120 ° C., between than 5 to 80° C., or between than 5 to 60° C.
  • the oxide conversion step 300 may result in a chemical reaction with oxides on a silicon germanium substrate having an oxide as follows:
  • the oxide may be converted into a solid ammonium-hexafluorosilicate compound and a solid ammonium-hexafluorogermanate compound on the substrate.
  • the oxide sublimation step 400 is illustrated in FIG. 5 .
  • the oxide sublimation step 400 comprises a first heating step 410 , or a second heating step 420 , or both.
  • the first heating step 410 may comprise heating the substrate to a temperature greater than 125° C., greater than 100° C., or greater than 90° C.
  • the result of the first step 410 may be sublimation of the solid ammonium-hexafluorosilicate compound according to the following reaction:
  • the gaseous products may then be removed from the reaction chamber.
  • the second heating step 420 may comprise heating the substrate to a higher temperature than that of the first heating step 410 .
  • the temperature may be greater than 275° C., greater than 250° C., or greater than 225° C.
  • a high temperature showerhead may be designed to heat up to 250° C.-300° C. without heating up the reaction chamber.
  • the result of the second step 420 may be sublimation of the solid ammonium-hexafluorogermanate compound according to the following reaction:
  • the gaseous products may then be removed from the reaction chamber.
  • the carbon removal step 500 is illustrated in FIG. 6 .
  • the carbon removal step 500 comprises a step 510 of flowing hydrogen precursors and other gaseous precursors into a remote plasma unit and a step 520 of flowing generated radicals and an optional additional precursor onto a substrate.
  • the first heating step 510 may comprise flowing argon, hydrogen, and ammonia into the remote plasma unit.
  • the gases may be flowed for a duration ranging between 0.1 and 180 seconds, between 1 and 120 seconds, or between 10 and 90 seconds. As a result, hydrogen radicals are generated in the remote plasma unit.
  • the step 520 takes the generated hydrogen radicals to react with carbon-based contaminants in the substrate. This step may happen at temperatures between 25° C. and 500° C., between 75° C. and 400° C., or between 150° C. and 300° C. A higher temperature showerhead may allow to heat up substrate and leading to effective removal of carbon.
  • the result of the step 520 may be removal of the carbon according to the following reaction:
  • Other reactions may include carbon with oxygen radicals.
  • the gaseous products may then be removed from the reaction chamber.

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Abstract

A system and method for removing both carbon-based contaminants and oxygen-based contaminants from a semiconductor substrate within a single process chamber is disclosed. The invention may comprise utilization of remote plasma units and multiple gas sources to perform the process within the single process chamber.

Description

    CROSS-REFERENCE TO RELATED PATENT APPLICATION
  • The present disclosure claims the benefit of U.S. Provisional Patent Application No. 62/532,248, filed on Jul. 13, 2017 and entitled “APPARATUS AND METHOD FOR REMOVAL OF OXIDE AND CARBON FROM SEMICONDUCTOR FILMS IN A SINGLE PROCESSING CHAMBER,” which is incorporated herein by reference.
    • FIELD OF INVENTION
  • The present disclosure generally relates to an apparatus and a method for manufacturing electronic devices. More particularly, the disclosure relates to removal of oxide and carbon within semiconductor films formed in a processing chamber.
    • BACKGROUND OF THE DISCLOSURE
  • Prior to the fabrication of semiconductor device, a clean surface of a wafer or substrate is desired. Contaminates on the substrate may adversely affect mechanical and electrical properties of the semiconductor devices formed. It is desired that these contaminates be removed before particular films are deposited onto the substrate.
  • Contaminants that exist on a silicon or silicon germanium substrate may include carbon-based contaminants, such as carbonaceous contaminants and hydrocarbon contaminates. Other contaminants may include oxygen-based contaminants, such as native oxides, for example. It may be imperative to remove these contaminants before epitaxial processes can take place.
  • Prior approaches to contaminant removal focus on removing one of the contaminants, either carbon-based or oxygen-based, but not both. This may be in part due to equipment limitations of the prior approaches. As a result, a system and method to remove both carbon-based and oxygen-based contaminants is desired.
  • BRIEF DESCRIPTION OF THE DRAWING FIGURES
  • These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the drawings of certain embodiments, which are intended to illustrate and not to limit the invention.
  • FIG. 1 is a cross-sectional illustration of a system in accordance with at least one embodiment of the invention.
  • FIG. 2 is a cross-sectional illustration of a system in accordance with at least one embodiment of the invention.
  • FIGS. 3A, 3B and 3C are flowcharts of methods in accordance with at least one embodiment of the invention.
  • FIG. 4 is a flowchart of a step in accordance with at least one embodiment of the invention.
  • FIG. 5 is a flowchart of a step in accordance with at least one embodiment of the invention.
  • FIG. 6 is a flowchart of a step in accordance with at least one embodiment of the invention.
    • DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
  • Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.
  • Embodiments of the invention are directed to a system with a single process chamber having a capability to remove both carbon-based contaminants and oxygen-based contaminants. The embodiments have several advantages over prior approaches including: (1) incorporation of at least one remote plasma unit (RPU) with the ability to generate both hydrogen radicals and fluorine radicals; and (2) compatibility of the process chamber with both hydrogen radicals and fluorine radicals.
  • Embodiments of the invention may be used to clean semiconductor substrates made of at least one of the following materials: silicon; silicon germanium; or germanium, for example. In one embodiment, the percentage of germanium in silicon germanium may vary from 10% to 90%. Also, embodiments of the invention may be used to etch carbon layers, such as an advanced patterning film (APF); photoresists; or other carbon contaminations including CHFx, SiC, or SiOC. In addition, embodiments of the invention may be used to clean a surface of dielectric materials, such as silicon oxide, silicon nitride, silicon oxynitride, fluorinated silicon oxide, silicon carboxide, and silicon carboxynitride. Furthermore, embodiments of the invention may be applied to patterned wafer surfaces.
  • FIG. 1 illustrates a system 100 in accordance with at least one embodiment of the invention. The system 100 may comprise a reaction chamber 110, a susceptor 120, a showerhead 130, a remote plasma unit 140, and a transport path 145 between the remote plasma unit 140 and the reaction chamber 110. A substrate 150 is placed on the susceptor 120 for processing.
  • The reaction chamber 110 defines a space in which the substrate 150 is processed. The reaction chamber 110, the susceptor 120, the showerhead 130, and the transport path 145 may be coated with materials or bulk ceramic material in order to allow for compatibility with different radicals. The materials for coating may include at least one of: anodized aluminum oxide (Al2O3); atomic layer deposition (ALD)-formed aluminum oxide; plasma sprayed Al2O3; bare aluminum parts with native aluminum oxide, yttrium oxide (Y2O3); yttrium oxide stabilized zirconium oxide (YSZ); zirconium oxide (ZrO2); lanthanum zirconium oxide (LZO); yttrium aluminum garnet (YAG); yttrium oxyfluoride (YOF); combination of the above materials; or the above substrate doped with other glass phase materials. In some cases, the coating materials can be made with two layers. For example, the first layer may be coated with anodized Al2O3 and the second layer may be coated with ALD-formed Al2O3. The coating may be amorphous phase, crystalline phase, or mixed. The bulk ceramic material may include: aluminum oxide (Al2O3); zirconium oxide (ZrO2); yttrium oxide (Y2O3); or yttrium oxide stabilized zirconium oxide (YSZ).
  • The system 100 also may comprise a first gas source 160, a second gas source 170, a third gas source 180, and a fourth gas source 190, which all may provide gas to the remote plasma unit 140. The remote plasma unit 140 may comprise a Paragon H* remote plasma unit from MKS Instruments, for example. The third gas source 180 may also be configured to provide gas directly into the reaction chamber 110 without going through the remote plasma unit 140. The first gas source 160 may comprise a source of a precursor gas that produces fluorine radicals, such as NF3, CF4, C2F6, C4F6, C4F8, COF2, SF6, or WF6, for example. The second gas source 170 may comprise a source of a gas that produces hydrogen radicals, such as H2, NH3, or H2O, for example. The second gas source 170 may comprise a gas that produces oxygen radicals, such as oxygen or ozone, for example. The third gas source 180 may be a source of NH3. The fourth gas source 190 may be a source of an inert gas, such as argon, helium, nitrogen, or neon, for example.
  • The remote plasma unit 140 generates radicals provided from the gas sources. The generated radicals then enter the reaction chamber 110 through the showerhead 130 and then flow onto the substrate 150. The remote plasma source may include: a toroidal style ICP source or a coil style ICP source driven by different RF frequencies, such as a 400 kHz, 2 MHz, 60 MHz and 2.56 GHz microwave source.
  • FIG. 2 illustrates a system 200 in accordance with at least one embodiment of the invention. The system 200 may comprise a reaction chamber 210, a susceptor 220, a showerhead 230, a first remote plasma unit 240 dedicating for oxide removal with F*, a second remote plasma unit 245 dedicating for carbon removal with H*, a transport path 246 below the first remote plasma unit, and a transport path 247 below the second remote plasma unit. A substrate 250 is placed on the susceptor 220 for processing. The system 200 may also comprise a first gate vale 248 and a second gate valve 249.
  • The reaction chamber 210 defines a space in which the substrate 250 is processed. The reaction chamber 210, the susceptor 220, and the showerhead 230 may be coated with materials or bulk ceramic material in order to allow for compatibility with different radicals, such as: anodized aluminum oxide (Al2O3); atomic layer deposition (ALD)-formed aluminum oxide; plasma sprayed Al2O3; bare aluminum parts with native aluminum oxide; yttrium oxide (Y2O3); yttrium oxide stabilized zirconium oxide (YSZ); zirconium oxide (ZrO2); lanthanum zirconium oxide (LZO); yttrium aluminum garnet (YAG); yttrium oxyfluoride (YOF); combination of the above materials; or the above substrate doped with other glass phase materials. In some cases, the coating materials may be made with two layers. For example, the first layer may be coated with anodized Al2O3 and the second layer may be coated with ALD-formed Al2O3. The coating may be amorphous phase, crystalline phase, or mixed. The bulk ceramic material may include: aluminum oxide (Al2O3); zirconium oxide (ZrO2); yttrium oxide (Y2O3); or yttrium oxide-stabilized zirconium oxide (YSZ). Besides the above coatings and bulk materials for different radicals, materials for the transport path 247 below the second remote plasma unit may also comprise bulk quartz material.
  • The system 200 also may comprise a first gas source 260, a second gas source 270, a third gas source 280, and a fourth gas source 290, which all may provide gas to the first remote plasma unit 240 and the second remote plasma unit 245. The first remote plasma unit 240 and the second remote plasma unit 245 may comprise a toroidal style ICP source or a coil style ICP source driven by different RF frequencies, such as a 400 kHz, 2 MHz, 60 MHz and 2.56 GHz microwave source, for example. The third gas source 280 may also be configured to provide gas directly into the reaction chamber 210 without going through the first remote plasma unit 240 or the second remote plasma unit 245. The first gas source 260 may comprise a source of a precursor gas that produces fluorine radicals, such as NF3, CF4, C2F6, C4F6, C4F8, COF2, SF6, or WF6, for example. The second gas source 270 may comprise a source of gas that produces hydrogen radicals, such as H2, NH3, or H2O, for example. The second gas source 270 may comprise a gas that produces oxygen radicals, such as oxygen or ozone, for example. The third gas source 280 may be a source of NH3. The fourth gas source 290 may be a source of an inert gas, such as argon, helium, nitrogen, or neon, for example.
  • The first remote plasma unit 240 (which may be dedicated for F* radicals) and the second remote plasma unit 245 (which may be dedicated for H* radicals) generate radicals provided from the gas sources. The generated radicals then enter the reaction chamber 210 through the showerhead 230 and then flow onto the substrate 250. To prevent radicals generated by one remote plasma unit back streaming into the second remote plasma, the gate valves 248 and 249 may be located at the outlet of RPU.
  • FIG. 3A illustrates a method in accordance with at least one embodiment of the invention. The method comprises an oxide conversion step 300, an oxide sublimation step 400, and a carbon removal step 500. Any of these steps or any combination of these steps may be repeated as needed. The entire method may be repeated through a repeat cycle 600.
  • FIG. 3B illustrates a method in accordance with at least one embodiment of the invention. The method comprises a carbon removal step 500, an oxide conversion step 300, and an oxide sublimation step 400. Any of these steps or any combination of these steps may be repeated as needed. The entire method may be repeated through a repeat cycle 600. The method of FIG. 3B differs from that of FIG. 3A in that the carbon removal step 500 comes before the oxide conversion step 300.
  • FIG. 3C illustrates a method in accordance with at least one embodiment of the invention. The method comprises a carbon removal step 500, an oxide conversion step 300, an oxide sublimation step 400, and a carbon removal step 500. Any of these steps or any combination of these steps may be repeated as needed. The entire method may be repeated through a repeat cycle 600. The method of FIG. 3C differs from that of FIG. 3B in that an additional carbon removal step 500 comes after the oxide sublimation step 400.
  • In accordance with at least one embodiment of the invention, the oxide conversion step 300 is illustrated in FIG. 4. The oxide conversion step 300 may comprises a step 310 of flowing gaseous precursors into a remote plasma unit and a step 320 of flowing generated radicals and an additional precursor onto a substrate. In accordance with at least one embodiment of the invention, the step 310 may comprise flow of argon, hydrogen, and NF3 into the remote plasma unit. A flow of argon may range between 0.01 and 20 slm, between 0.1 and 10 slm, or between 1 and 8 slm. A flow of hydrogen may range between 10 sccm and 1500 slm, between 25 and 1200 slm, or between 50 sccm and 1000 slm. A flow of NF3 may occur for a particular amount of time while the plasma is on in the remote plasma unit, ranging between 0.1 and 120 seconds, between 1 and 100 seconds, or between 5 and 80 seconds. The step 310 may comprise heating the reaction chamber 210 to a temperature between than 5 to 120° C., between than 5 to 80° C., or between than 5 to 60° C.
  • As a result of step 310, a gas of fluorine radicals is generated in the remote plasma unit. The fluorine radicals leave the remote plasma unit and may combine with an optional additional precursor gas in step 320 onto the substrate disposed in a reaction chamber. The optional additional precursor gas may comprise ammonia flowed at a rate ranging between 10 sccm and 1500 slm, between 25 and 1200 slm, or between 50 sccm and 1000 slm. The step 320 may comprise heating the reaction chamber 210 to a temperature between than 5 to 120 ° C., between than 5 to 80° C., or between than 5 to 60° C. The oxide conversion step 300 may result in a chemical reaction with oxides on a silicon germanium substrate having an oxide as follows:

  • NH4F(g)+SiGeOx(s)→(NH4)2SiF6(s)+(NH4)2GeF6(s)+H2O(g)
  • As a result of the oxide conversion step 300, the oxide may be converted into a solid ammonium-hexafluorosilicate compound and a solid ammonium-hexafluorogermanate compound on the substrate.
  • In accordance with at least one embodiment of the invention, the oxide sublimation step 400 is illustrated in FIG. 5. The oxide sublimation step 400 comprises a first heating step 410, or a second heating step 420, or both. The first heating step 410 may comprise heating the substrate to a temperature greater than 125° C., greater than 100° C., or greater than 90° C. The result of the first step 410 may be sublimation of the solid ammonium-hexafluorosilicate compound according to the following reaction:

  • (NH4)2SiF6(s)→NH3(g)+HF(g)+SiF4(g)
  • The gaseous products may then be removed from the reaction chamber.
  • The second heating step 420 may comprise heating the substrate to a higher temperature than that of the first heating step 410. The temperature may be greater than 275° C., greater than 250° C., or greater than 225° C. To reach the high operation temperature, a high temperature showerhead may be designed to heat up to 250° C.-300° C. without heating up the reaction chamber. The result of the second step 420 may be sublimation of the solid ammonium-hexafluorogermanate compound according to the following reaction:

  • (NH4)2GeF6(s)→NH3(g)+HF(g)+GeF4(g)
  • The gaseous products may then be removed from the reaction chamber.
  • In accordance with at least one embodiment of the invention, the carbon removal step 500 is illustrated in FIG. 6. The carbon removal step 500 comprises a step 510 of flowing hydrogen precursors and other gaseous precursors into a remote plasma unit and a step 520 of flowing generated radicals and an optional additional precursor onto a substrate. The first heating step 510 may comprise flowing argon, hydrogen, and ammonia into the remote plasma unit. The gases may be flowed for a duration ranging between 0.1 and 180 seconds, between 1 and 120 seconds, or between 10 and 90 seconds. As a result, hydrogen radicals are generated in the remote plasma unit.
  • The step 520 takes the generated hydrogen radicals to react with carbon-based contaminants in the substrate. This step may happen at temperatures between 25° C. and 500° C., between 75° C. and 400° C., or between 150° C. and 300° C. A higher temperature showerhead may allow to heat up substrate and leading to effective removal of carbon. The result of the step 520 may be removal of the carbon according to the following reaction:

  • C(s)+H*(g)→CxHy(g)
  • Other reactions may include carbon with oxygen radicals. The gaseous products may then be removed from the reaction chamber.
  • The particular implementations shown and described are illustrative of the invention and its best mode and are not intended to otherwise limit the scope of the aspects and implementations in any way. Indeed, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and/or physical couplings between the various elements. Many alternative or additional functional relationship or physical connections may be present in the practical system, and/or may be absent in some embodiments.
  • It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases.
  • The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems, and configurations, and other features, functions, acts, and/or properties disclosed herein, as well as any and all equivalents thereof.

Claims (21)

What is claimed is:
1. An apparatus for processing a semiconductor substrate comprising:
a reaction chamber;
a susceptor configured to hold a substrate;
a first gas source for providing a first gas;
a second gas source for providing a second gas;
a first remote plasma unit configured to receive the first gas and produce a first radical gas;
a gas distribution device configured to flow the first radical gas and the second gas onto the substrate; and
a transport path connecting the remote plasma unit to the gas distribution device, wherein the first radical gas passes through the gas distribution device onto the substrate;
wherein the gas distribution device, the reaction chamber, the transport path, and the susceptor are coated with at least one of: anodized aluminum oxide (Al2O3); atomic layer deposition (ALD)-formed aluminum oxide; plasma sprayed Al2O3; bare aluminum parts with native aluminum oxide; yttrium oxide (Y2O3); yttrium oxide stabilized zirconium oxide (YSZ); zirconium oxide (ZrO2); lanthanum zirconium oxide (LZO); yttrium aluminum garnet (YAG); yttrium oxyfluoride (YOF); aluminum oxide (Al2O3); zirconium oxide (ZrO2); yttrium oxide (Y2O3); or yttrium oxide stabilized zirconium oxide (YSZ).
2. The apparatus of claim 1, wherein the first gas comprises at least one of: NF3, CF4, C2F6, C4F6, C4F8, COF2, SF6, or WF6.
3. The apparatus of claim 1, wherein the second gas comprises at least one of: H2, NH3, H2O, O2, or O3.
4. The apparatus of claim 1, further comprising:
a third gas source for providing a third gas; and
a fourth gas source for providing a fourth gas.
5. The apparatus of claim 4, wherein the third gas comprises NH3.
6. The apparatus of claim 4, wherein the fourth gas comprises at least one of: argon, helium, nitrogen, or neon.
7. The apparatus of claim 1, wherein the first gas is used to remove an oxide from the substrate.
8. The apparatus of claim 1, wherein the second gas is used to remove carbon from the substrate.
9. The apparatus of claim 1, wherein the second gas passes through the first remote plasma unit and converts into a second radical gas.
10. The apparatus of claim 1, further comprising a second remote plasma unit configured to receive the second gas and produce a second radical gas.
11. The apparatus of claim 1, wherein the transport path comprises bulk quartz material.
12. A method for processing a semiconductor substrate comprising:
providing a reaction chamber and a susceptor configured to hold a substrate;
performing an oxide conversion step on the substrate, the oxide conversion step comprising: (1) flowing a first gas into a first remote plasma unit to form a first radical gas; and (2) flowing the first radical gas onto the substrate;
performing an oxide sublimation step on the substrate, the oxide sublimation step comprising: (1) a first heating step; and (2) a second heating step; and
performing a carbon removal step on the substrate;
wherein the oxide conversion step, the oxide sublimation step, and the carbon removal step are each performed in the reaction chamber; and
wherein any of the oxide conversion step, the oxide sublimation step, and the carbon removal step are repeated as needed.
13. The method of claim 12, wherein the carbon removal step comprises:
flowing a second gas into the first remote plasma unit to form a second radical gas; and
flowing the second radical gas onto the substrate.
14. The method of claim 12, wherein the carbon removal step comprises:
flowing a second gas into a second remote plasma unit to form a second radical gas; and
flowing the second radical gas onto the substrate.
15. The method of claim 12, wherein the first gas comprises at least one of: NF3, CF4, C2F6, C4F6, C4F8, COF2, SF6, or WF6.
16. The method of claim 13, wherein the second gas comprises at least one of: H2, NH3, H2O, O2, or O3.
17. A method for processing a semiconductor substrate comprising:
providing a reaction chamber and a susceptor configured to hold a substrate;
performing a carbon removal step on the substrate;
performing an oxide conversion step on the substrate, the oxide conversion step comprising: (1) flowing a first gas into a first remote plasma unit to form a first radical gas; and (2) flowing the first radical gas onto the substrate;
performing an oxide sublimation step on the substrate, the oxide sublimation step comprising: (1) a first heating step; and (2) a second heating step; and
wherein the carbon removal step, the oxide conversion step, and the oxide sublimation step are each performed in the reaction chamber; and
wherein any of the carbon removal step, the oxide conversion step, and the oxide sublimation step are repeated as needed.
18. The method of claim 17, wherein the carbon removal step comprises:
flowing a second gas into the first remote plasma unit to form a second radical gas; and
flowing the second radical gas onto the substrate.
19. The method of claim 17, wherein the carbon removal step comprises:
flowing a second gas into a second remote plasma unit to form a second radical gas; and
flowing the second radical gas onto the substrate.
20. The method of claim 17, wherein the first gas comprises at least one of: NF3, CF4, C2F6, C4F6, C4F8, COF2, SF6, or WF6.
21. The method of claim 18, wherein the second gas comprises at least one of: H2, NH3, H2O, O2, or O3.
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