`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Samsung Electronics Co., Ltd. v. Demaray LLC
`Samsung Electronic's Exhibit 1037
`Exhibit 1037, Page 1
`
`

`

`
`
`
`Patent Application Publication
`
`
`
`
`
`
`Feb. 13,2003 Sheet 1 of 12
`
`
`
`US 2003/0029563 Al
`
`
`
`
`
`
`
`
`
`EXHAUST
`
`
`i —— ——_oe
`
`
`
`RADICALS IN
`OUT
`
`
`
`FIG._ LA
`
`et IN}
`
`50
`
`Ex. 1037, Page 2
`
`Ex. 1037, Page 2
`
`

`

`
`
`Patent Application Publication
`
`
`
`
`
`
`
`
`
`Feb. 13,2003 Sheet 2 of 12
`
`
`
`US 2003/0029563 Al
`
`
`
`
`
`
`
`
`
`Ex. 1037, Page 3
`
`Ex. 1037, Page 3
`
`

`

`
`
`
`Patent Application Publication
`
`
`
`
`
`Feb. 13,2003 Sheet 3 of 12
`
`
`
`US 2003/0029563 Al
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Fie,3
`
`
`FIG. G
`
`
`
`
`
`
`
`
`
`Ex. 1037, Page 4
`
`Ex. 1037, Page 4
`
`

`

`
`
`
`Patent Application Publication
`
`
`
`
`
`Feb. 13,2003 Sheet 4 of 12
`
`
`
`US 2003/0029563 Al
`
`
`
`AIN
`
`
`
`
`ION
`CONCENTRATION
`
`
`
`(DEPTH)
`
`
`
`
`
`Fee, I
`
`
`
`Ex. 1037, Page 5
`
`Ex. 1037, Page 5
`
`

`

`
`
`Patent Application Publication
`
`
`
`
`
`
`
`Feb. 13,2003 Sheet 5 of 12
`
`
`
`US 2003/0029563 Al
`
`
`
`
`
`REEEERSSES
`PALLLLLLMAADPLIADLASoSSONNe
`SSSa
`
`“UULL
`held
`
`LPmy
`
`Ldetel
`
`=jse~tp&-=~~~_—
`
`~~,
`
`wieRoz/a~,~Ley
`
`SOld
`
`
`
`Ex. 1037, Page 6
`
`Ex. 1037, Page 6
`
`

`

`
`
`
`Patent Application Publication
`
`
`
`
`
`
`
`Feb. 13,2003 Sheet 6 of 12
`
`US 2003/0029563 Al
`
`
`
`
`
`Ex. 1037, Page 7
`
`Ex. 1037, Page 7
`
`

`

`
`
`
`
`
`
`US 2003/0029563 Al
`
`
`
`
`
`me
`
`Sites
`
`Feb. 13, 2003 Sheet 7 of 12
`
`Patent Application Publication
`
`Ex. 1037, Page 8
`
`Ex. 1037, Page 8
`
`

`

`
`
`Patent Application Publication
`
`
`
`
`
`
`
`
`
`Feb. 13,2003 Sheet 8 of 12
`
`US 2003/0029563 Al
`
`
`
`
`
`Ex. 1037, Page 9
`
`Ex. 1037, Page 9
`
`

`

`FG,
`
`
`
`
`
`
`
`
`
`Patent Application Publication
`
`
`
`
`
`
`
`Feb. 13,2003 Sheet 9 of 12
`
`
`
`US 2003/0029563 Al
`
`
`
`
`
`IA
`
`Ex. 1037, Page 10
`
`Ex. 1037, Page 10
`
`

`

`
`
`Patent Application Publication
`
`
`
`
`
`yea
`
`
`
`249:7Ke
`
`
`
`
`
`
`Feb. 13, 2003 Sheet 10 of 12
`
`
`
`US 2003/0029563 Al
`
`Ex. 1037, Page 11
`
`Ex. 1037, Page 11
`
`

`

`
`
`
`Patent Application Publication
`
`
`
`
`
`
`Feb. 13,2003 Sheet 11 of 12
`
`
`
`US 2003/0029563 Al
`
`
`
`LG.7E
`
`— —_|
`
`
`
`
`
`CLetenereekLe
`FIG.AO
`
`ee
`
`Ex. 1037, Page 12
`
`Ex. 1037, Page 12
`
`

`

`ora
`
`
`
`YD
`Q
`if!
`OP:
`L
`
`x9 9U
`
`e
`
`
`
`
`
`
`
`oO
`am1
`O
`oO.
`fe
`
`=o
`
`
`
`Patent Application Publication
`
`
`
`
`
`
`
`Feb. 13,2003 Sheet 12 of 12
`
`
`
`US 2003/0029563 Al
`
`Ex. 1037, Page 13
`
`gx
`=
`
`z<
`
`
`
`Ex. 1037, Page 13
`
`

`

`
`
`US 2003/0029563 Al
`
`
`
`Feb. 13, 2003
`
`
`
`CORROSION RESISTANT COATING FOR
`
`
`
`
`SEMICONDUCTOR PROCESSING CHAMBER
`
`
`
`
`
`BACKGROUND OF THE INVENTION
`
`
`
`
`
`
`
`
`
`
`[0001] The present invention relates to equipment used in
`
`
`
`
`
`
`
`the manufacture of semiconductor devices. More specifi-
`
`
`
`
`
`
`
`cally, the present invention relates to formation of a plasma-
`
`
`
`
`
`
`resistant coating on the surfaces of selected components of
`
`
`
`semiconductor manufacturing equipment.
`
`
`
`
`
`
`
`
`[0002] With the development of high density plasma
`
`
`
`
`
`
`
`
`sources and 300 mm-wafer-size reactors, and the growing
`
`
`
`
`
`
`
`importance of certain high temperature processing steps,
`
`
`
`
`
`
`
`wear on chamber materials may impact tool performance
`
`
`
`
`
`
`and productivity. Specifically, interaction between corrosive
`
`
`
`
`
`
`
`plasmasand reactor materials becomeofcritical importance
`
`
`
`
`
`
`
`to development of future product lines of semiconductor
`
`
`
`
`
`
`manufacturing equipment. Very harsh environments (e.g.,
`
`
`
`
`
`
`
`
`
`
`NF3, C3F,, C3F3, CIF, CF,, SiH,, TEOS, WF, NH, HBr,
`
`
`
`
`
`
`
`etc.) can be found in plasma etchers and plasma-enhanced
`
`
`
`
`
`
`
`deposition reactors. Constituents from many of these envi-
`
`
`
`
`
`
`
`
`
`ronments may react with and corrode parent anodized mate-
`rials such as aluminum oxide.
`
`
`
`
`
`
`
`
`
`
`
`[0003] Because of their favorable physical characteristics,
`
`
`
`
`
`
`
`ceramic materials are commonly used in today’s semicon-
`
`
`
`
`
`
`
`ductor manufacturing equipment to meet the high process
`
`
`
`
`
`
`performance standards demanded by integrated circuit
`
`
`
`
`
`
`manufacturers. Specifically, ceramic materials exhibit high
`
`
`
`
`
`
`
`resistance to corrosion, which helps to increase process kit
`
`
`
`
`
`
`
`lifetimes and lowers the cost of consumables as compared to
`
`
`
`
`
`
`other materials such as aluminum or quartz. Example of
`
`
`
`
`
`
`components that can be advantageously manufactured from
`
`
`
`
`
`
`
`ceramic materials include chamber domes for inductively
`
`
`
`
`
`
`
`
`
`coupled reactors, edge rings used to mask the edge of a
`
`
`
`
`
`
`
`substrate support in certain processing chambers, and cham-
`
`
`
`
`
`
`
`
`
`
`ber liners that protect walls of the chamber from direct
`
`
`
`
`
`
`
`
`exposure to plasma formed within the chamber and improve
`
`
`
`
`
`
`plasma confinement by reducing coupling of a plasma with
`
`
`
`
`
`
`
`conductive chamber walls. In some instances, the chamber
`
`
`
`
`
`
`
`walls themselves may also be manufactured from ceramic
`materials. Ceramic materials are also used for critical com-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`ponents such as high temperature heaters and electrostatic
`chucks.
`
`
`
`
`
`
`
`
`
`
`aluminum fluoride (AIF,) is approximately 600° C. If a
`
`
`
`
`
`ceramic component is employed at a temperature exceeding
`
`
`
`
`
`
`
`
`
`the sublimation temperature, the outer surface of the com-
`
`
`
`
`
`
`
`ponent may be consumed by the process of formation of
`
`
`
`
`
`
`
`
`AlO:F, AIF, or AICI. This consumption of material can
`
`
`
`
`
`
`
`degrade the chamber component and/or introduce particles
`
`
`
`into the process.
`
`
`
`
`
`
`
`[0006]
`In light of the above, improvementin the corrosion
`
`
`
`
`
`
`resistance of various substrate processing chamberparts and
`
`
`components is desirable.
`SUMMARYOF THE INVENTION
`
`
`
`
`
`
`
`
`
`invention provides a method for
`[0007] The present
`
`
`
`
`
`
`improving the corrosion resistance of components of semi-
`
`
`
`
`
`
`
`conductor tools by creating high temperature halogen cor-
`
`
`
`
`
`
`
`rosion resistant surface coatings. Specifically, coatings of
`
`
`
`
`
`
`
`
`rare earth-containing materials are formed over the surfaces
`
`
`
`
`
`
`
`of ceramic tool components. These rare earth-containing
`
`
`
`
`
`
`
`
`materials are stable in plasma environments at high tem-
`
`
`
`
`
`
`
`
`peratures and may be formed onto the chamber components
`
`
`
`
`
`
`
`by sputter deposition. To promote adhesion of the coating to
`
`
`
`
`
`
`
`
`the parent material, an adhesion layer maybefirst formed on
`
`
`
`
`
`
`
`
`
`the ceramic material by accelerating rare earth ions into the
`
`
`
`
`
`
`
`surface of the ceramic material at changed energies to form
`
`
`
`
`
`
`
`
`an implant layer prior to formation of the surface coating.
`
`
`
`
`
`
`[0008] An embodimentof a substrate processing chamber
`
`
`
`
`
`
`
`
`in accordance with the present invention includes at least
`
`
`
`
`
`
`one component bearing a rare earth-containing coating
`
`
`
`
`
`
`bound to a parent material by an intervening adhesion layer,
`
`
`
`
`
`
`
`
`such that the component exhibits resistance to etching in a
`
`
`plasma environment.
`
`
`
`
`
`
`[0009] An embodiment of a method for treating a parent
`
`
`
`
`
`
`material for resistance to plasma etching comprises forming
`
`
`
`
`
`
`
`
`an adhesion layer over a parent material, and forming a rare
`
`
`
`
`
`
`earth-containing coating over the adhesion layer.
`
`
`
`
`
`
`
`[0010] These and other embodimentsof the present inven-
`
`
`
`
`
`
`
`
`tion, as well as its advantages and features, are described in
`
`
`
`
`
`
`
`
`
`more detail in conjunction with the text below and attached
`
`figures.
`
`
`
`
`
`
`
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`
`
`
`
`
`
`
`
`
`
`
`Ideally, critical and/or high value ceramic parts of
`[0004]
`
`
`
`
`
`[0011] FIG. 1A is a simplified cross-sectional view of a
`
`
`
`
`
`
`a semiconductor processing tool employed in production
`
`
`
`
`
`
`
`high density plasma chemical vapor deposition chamber;
`
`
`
`
`
`
`
`
`should havealifetime of at least one year. Depending on the
`
`
`
`
`
`
`
`particular tool, this can correspond to processing of 50,000
`
`
`
`
`
`[0012] FIG. 1B is a simplified cross-sectional view of a
`
`
`
`
`
`
`
`
`wafers or more without changing any parts on thetool (ie.,
`
`
`
`
`
`
`
`capacitively coupled plasma enhanced chemical vapor depo-
`
`
`
`
`
`
`
`
`
`a zero consumable situation), while at the same time main-
`
`
`sition chamber;
`
`
`
`
`
`
`
`taining high process performancestandards. For example, to
`
`
`
`
`
`
`[0013] FIG. 2A is a cross-sectional view of a coated
`
`
`
`
`
`
`
`meet the requirements of some manufacturers, less than 20
`member in accordance with a first embodiment of the
`
`
`
`
`
`
`
`
`
`
`
`
`particles of size of greater than 0.2 wm should be added to
`
`
`present invention;
`
`
`
`
`
`
`
`
`the wafer during the processing of the wafer in the chamber.
`
`
`
`
`
`
`
`
`
`
`
`
`[0014] FIG. 2B is a cross-sectional view of a coated
`[0005] However, unwanted particle generation is an issue
`member in accordance with a second embodiment of the
`
`
`
`
`
`
`
`
`
`
`
`
`for high temperature applications where processing tem-
`
`
`
`
`
`
`
`
`
`present invention;
`peratures exceed 550° C. For example, in highly corrosive
`
`
`
`
`
`
`
`
`fluorine and chlorine environments, Al,O, and AIN ceramic
`
`
`
`
`
`[0015] FIG. 3 is a simplified schematic view of a Metal
`
`
`
`
`
`
`
`materials may corrode to form unwanted AlO:F, AIF,, or
`
`
`
`
`
`Plasma
`Immersion Jon
`Implantation and Deposition
`
`
`
`
`
`
`
`
`AlCl films at the component surface. These AlO:F, AIF,,, or
`
`
`(MEPIIID) technique;
`
`
`
`
`
`
`
`
`
`AICL, films have relatively high vapor pressures and rela-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`FIG.4 is a graph illustrating the concentration of
`[0016]
`tively low sublimation temperatures. For example, the sub-
`
`
`
`
`
`
`
`
`
`
`
`
`
`limation temperature of aluminum chloride (AICL,)
`is
`rare earth ions at various depths in a ceramic component
`
`
`
`
`
`
`
`
`
`treated with MEPIIID;
`approximately 350° C. and the sublimation temperature of
`
`
`
`
`
`
`
`
`
`
`Ex. 1037, Page 14
`
`Ex. 1037, Page 14
`
`

`

`
`
`US 2003/0029563 Al
`
`
`
`Feb. 13, 2003
`
`
`
`
`
`
`
`
`
`
`[0037] FIG. 10B showsa further magnified (7500x) view
`
`
`
`
`
`
`
`of the fractured AIN coupon of FIG. 10A.
`
`
`
`
`
`
`
`
`[0038] FIG. 11 shows the results of Energy Dispersive
`
`
`
`
`
`
`
`Spectroscopy (EDS) of the surface of the AIN coupon of
`FIGS. 10A-10B coated in accordance with an embodiment
`
`
`
`
`
`
`
`
`
`
`
`
`
`of the present invention, following exposure to a fluorine
`
`
`
`ambient at high temperature.
`
`
`
`DESCRIPTION OF THE SPECIFIC
`
`
`EMBODIMENTS
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0017] FIG. 5 is a simplified cross-sectional view of an
`
`
`
`
`
`
`
`
`exemplary metal vapor vacuum arc implanter used in the
`
`
`MEPIIID technique;
`
`
`
`
`
`[0018] FIG. 6 is a simplified schematic view of an Ion
`
`
`
`
`
`Bombardment Assisted Deposition (IBAD) technique;
`
`
`
`
`
`
`
`[0019] FIG. 7A shows a magnified (2000x) view of the
`
`
`
`
`
`
`
`
`
`top surface of a first grade of an AIN coupon following
`
`
`
`
`
`exposure to a fluorine ambient at high temperature.
`
`
`
`
`
`
`[0020] FIG. 7B shows a further magnified (7500x) view
`
`
`
`
`
`
`
`
`
`of the top surface of the AIN coupon of FIG. 7A.
`
`
`
`
`
`
`
`[0039] According to the present invention, ceramic com-
`
`
`
`
`
`
`
`[0021] FIG. 7C shows a magnified (2000x) view of the
`
`
`
`
`
`
`ponents of semiconductor fabrication tools, including but
`
`
`
`
`
`
`
`top surface of a second grade of an AIN coupon following
`
`
`
`
`
`
`
`
`not limited to electrostatic chucks, gas nozzles, chamber
`
`
`
`
`
`exposure to a fluorine ambient at high temperature.
`
`
`
`
`
`
`
`domes, heated pedestals, gas distribution manifolds, cham-
`
`
`
`
`
`
`
`
`
`ber walls and chamber liners, may be coated with a rare
`
`
`
`
`
`
`[0022] FIG. 7D showsa further magnified (7500x) view
`
`
`
`
`
`
`
`earth-containing material and adhesion layer in order to
`
`
`
`
`
`
`
`
`
`of the top surface of the AIN coupon of FIG. 7C.
`
`
`
`
`
`
`
`improve corrosion resistance. Environments for which the
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0023] FIG. 8A shows a magnified (2000x) view of the
`coated components can be advantageously used include, but
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`top surface of a first grade of an AIN coupon coated with
`are not limited to, highly corrosive plasmaetching environ-
`
`
`
`
`
`
`
`
`
`
`
`
`
`yttrium oxide by reactive sputtering in accordance with an
`ments, and high temperature deposition environments that
`
`
`
`
`
`
`
`
`alternative embodimentof the present invention.
`feature corrosive gases.
`
`
`
`
`
`
`
`
`
`
`
`
`[0024] FIG. 8B shows a further magnified (7500x) view
`[0040]
`I. Exemplary Substrate Processing Chambers
`
`
`
`
`
`
`
`
`
`of the top surface of the AIN coupon of FIG. 8A.
`
`
`
`
`
`[0041] FIGS. 1A and 1B are simplified cross-sectional
`
`
`
`
`
`
`
`[0025] FIG. 8C shows a magnified (2000x) view of the
`
`
`
`
`
`
`views of exemplary substrate processing chambers in which
`
`
`
`
`
`
`
`
`
`top surface of the AIN coupon of FIGS. 8A-B following
`
`
`
`
`
`
`
`ceramic components made according to the method of the
`
`
`
`
`
`exposure to a fluorine ambient at high temperature.
`
`
`
`
`
`
`present invention may be employed. FIG.1A is a simplified
`
`
`
`
`
`
`
`cross-sectional view of a high density plasma chemical
`
`
`
`
`
`
`[0026] FIG. 8D shows a magnified (7500x) view of the
`
`
`
`
`
`
`vapor deposition (HDP-CVD)chamber 10 such as an Ultima
`
`
`
`
`
`
`
`top surface of the AIN coupon of FIG. 8C.
`
`
`
`
`
`HDP-CVDsubstrate processing chamber manufactured by
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`[0027] FIG. 8E shows a magnified (2000x) view of the
`Applied Materials, the assignee of the present invention. In
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`top surface of a second grade of an AIN coupon coated with
`FIG. 1A, substrate processing chamber 10 includes a
`
`
`
`
`
`
`yttrium oxide by reactive sputtering in accordance with an
`
`
`
`
`
`vacuum chamber 12 in which a substrate support/heater 14
`
`
`
`
`
`
`
`
`
`
`
`alternative embodimentof the present invention.
`is housed. Substrate support/heater 14 includes an electro-
`
`
`
`
`
`
`
`static chuck 15 that securely clamps substrate 16 to substrate
`
`
`
`
`
`
`[0028] FIG. 8F showsa further magnified (7500x) view
`
`
`
`
`support/heater 14 during substrate processing.
`
`
`
`
`
`
`
`
`
`
`of the top surface of the coated AIN coupon of FIG. 8E.
`
`
`
`
`
`[0042] Whensubstrate support/heater 14 is in a processing
`
`
`
`
`
`
`
`[0029] FIG. 8G shows a magnified (2000x) view of the
`
`
`
`
`
`
`
`
`position (indicated by dotted line 18), deposition and carrier
`
`
`
`
`
`
`
`
`top surface of an AIN coupon coated with in accordance with
`
`
`
`
`
`
`
`
`
`gases are flowed into chamber 10 via gas injection nozzles
`
`
`
`
`
`
`
`one embodiment of the present invention, following expo-
`
`
`
`
`
`
`
`
`
`20. Nozzles 20 receive gases through gas supply lines,
`
`
`
`
`
`sure to a fluorine ambient at high temperature.
`
`
`
`
`
`
`
`
`which are not shown. Chamber 10 can be cleaned by the
`introduction offluorine radicals or other etchant radicalsthat
`
`
`
`
`
`
`[0030] FIG. 8H showsa further magnified (7500x) view
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`of the top surface of the AIN coupon of FIG. 8G.
`are dissociated in a remote microwave plasma chamber (not
`
`
`
`
`
`
`
`
`shown) and delivered to chamber 10 through a gas feed port
`
`
`
`
`
`
`
`[0031] FIG. 9A shows a magnified (2000x) view of the
`
`
`
`
`
`
`
`
`22. Unreacted gases and reaction byproducts are exhausted
`
`
`
`
`
`
`
`
`
`top surface of an AIN coupon implanted with yttrium in
`
`
`
`
`
`
`
`from the chamber 10 by a pump 24 through an exhaust port
`
`
`
`
`
`
`
`accordance with one embodimentof the present invention.
`
`
`
`
`
`
`on the bottom of the chamber. Pump 24 can beisolated from
`
`
`
`
`
`
`
`
`
`
`
`[0032] FIG. 9B shows a further magnified (7500x) view
`chamber 10 by a gate valve 26.
`
`
`
`
`
`
`
`
`
`
`of the top surface of the implanted AIN coupon of FIG. 9A.
`
`
`
`
`
`
`
`
`
`[0043] The rate at which deposition, carrier and clean
`
`
`
`
`
`
`
`[0033] FIG. 9C shows a further magnified (9000x) view
`
`
`
`
`
`
`gases are supplied to chamber 10 is controlled by a mass
`
`
`
`
`
`
`
`of the fractured AIN coupon of FIGS. 9A-9B.
`
`
`
`
`
`
`
`
`
`flow controllers and valves (not shown), which are in turn
`
`
`
`
`
`
`
`controlled by computer processor (not shown). Similarly, the
`
`
`
`
`
`
`
`[0034] FIG. 9D shows a magnified (2000x) view of the
`
`
`
`
`
`
`
`
`
`rate at which gases are exhausted from the chamber is
`
`
`
`
`
`
`
`
`
`surface of the implanted AIN coupon of FIGS. 9A-9C
`
`
`
`
`
`
`
`
`controlled byathrottle valve 28 and gate valve 26, which are
`
`
`
`
`
`
`following exposure to a fluorine ambient at high tempera-
`
`
`
`
`
`also controlled by the computer processor.
`ture.
`
`
`
`
`
`
`
`
`
`[0044] Aplasma can be formed from gases introduced into
`
`
`
`
`
`chamber 10 by application of RF energy to independently
`
`
`
`
`
`
`
`
`
`controlled top coil 30 and side coil 32. Coils 30 and 32 are
`
`
`
`
`
`
`
`
`mounted on a chamber dome 34, which defines the upper
`
`
`
`
`
`
`
`boundary of vacuum chamber 12. The lower boundary of
`
`
`
`
`
`
`
`vacuum chamber 12 is defined by chamber walls 36. Sub-
`
`
`
`
`
`
`
`[0035] FIG. 9E shows a further magnified (7500x) view
`
`
`
`
`
`
`
`
`
`of the surface of the implanted AIN coupon of FIG. 9D.
`
`
`
`
`
`
`
`[0036] FIG. 10A shows a magnified (3300x) view of a
`
`
`
`
`
`
`
`
`fractured AIN coupon implanted with yttrium oxide follow-
`
`
`
`
`
`
`ing exposure to a fluorine ambient at high temperature.
`
`
`
`Ex. 1037, Page 15
`
`Ex. 1037, Page 15
`
`

`

`
`
`US 2003/0029563 Al
`
`
`
`Feb. 13, 2003
`
`
`
`[0051]
`
`strates can be loaded into chamber 10 and onto chuck 15
`
`
`
`
`
`
`
`
`
`
`
`
`
`through an opening 38 in chamber wall 36.
`
`
`
`
`
`
`
`
`[0045] According to the present invention, any or all of
`
`
`
`
`
`
`
`
`
`electrostatic chuck 15, gas nozzles 20, and chamber dome 34
`
`
`
`
`
`
`
`of substrate support/heater 14 may be fabricated from mate-
`
`
`
`
`
`rial implanted with rare-earth ions.
`
`
`
`
`
`[0046] FIG. 1B is a simplified cross-sectional view of a
`
`
`
`
`
`capacitively-coupled plasma enhanced chemical vapor
`
`
`
`
`
`
`
`deposition chamber (PECVD) 50 such as the CxZ CVD
`
`
`
`
`
`
`substrate processing chamber manufactured by Applied
`
`
`
`
`
`
`
`
`Materials, the assignee of the present invention. In FIG. 1B,
`
`
`
`
`
`
`substrate processing chamber 50 includes a vacuum cham-
`
`
`
`
`
`
`
`ber 52 in which a heated pedestal 54 and a gas distribution
`
`
`
`
`
`
`manifold 56 are housed. During processing, a substrate 58
`
`
`
`
`
`
`
`(e.g., a semiconductor wafer) is positioned on a flat or
`
`
`
`
`
`
`
`
`
`slightly convex surface 54A of pedestal 54. The pedestal can
`
`
`
`
`
`
`
`be controllably moved between a substrate loading position
`
`
`
`
`
`
`
`(depicted in FIG. 1B) and a substrate processing position
`
`
`
`
`
`
`
`
`(indicated by dashed line 60 in FIG. 1B), which is closely
`
`
`
`adjacent to manifold 56.
`
`
`
`
`
`
`
`
`[0047] Deposition, carrier and cleaning gases are intro-
`
`
`
`
`
`
`
`
`duced into chamber52 through perforated holes 56A ofa gas
`
`
`
`
`
`
`
`distribution faceplate portion of manifold 56. More specifi-
`
`
`
`
`
`
`
`
`
`
`cally, gases input from external gas sources (not shown) flow
`
`
`
`
`
`
`
`
`
`
`into the chamber through the inlet 62 of manifold 56,
`
`
`
`
`
`
`
`through a conventional perforated blocker plate 64 and then
`
`
`
`
`
`
`
`
`through holes 56A of the gas distribution faceplate. Gases
`
`
`
`
`
`
`
`are exhausted from chamber 52 through an annular, slot-
`
`
`
`
`
`
`
`
`
`shaped orifice 70 surrounding the reaction region and then
`
`
`
`
`
`
`
`into an annulate exhaust plenum 72. Exhaust plenum 72 and
`
`
`
`
`
`
`slot-shapedorifice 70 are defined by ceramic chamberliners
`
`
`
`
`
`
`74 and 76 and by the bottom of chamberlid 57.
`
`
`
`
`
`
`
`
`
`[0048] The rate at which deposition, carrier and clean
`
`
`
`
`
`
`
`gases are supplied to chamber50 is controlled by mass flow
`
`
`
`
`
`
`
`
`
`controllers and valves (not shown), which are in turn con-
`
`
`
`
`
`
`
`trolled by computer processor (not shown). Similarly, the
`
`
`
`
`
`
`
`
`
`rate at which gases are exhausted from the chamber is
`
`
`
`
`
`
`
`
`controlled by a throttle valve (not shownand also controlled
`
`
`
`
`
`
`
`
`by the computer processor) connected to exhaust port 66,
`
`
`
`
`
`whichis fluidly-coupled to exhaust plenum 72.
`
`
`
`
`
`
`
`[0049] The deposition process in chamber 50 can beeither
`
`
`
`
`
`
`
`a thermal or a plasma-enhanced process.
`In a plasma-
`
`
`
`
`
`
`
`enhancedprocess, an RF powersupply (not shown) provides
`
`
`
`
`
`
`
`
`electrical energy between the gas distribution faceplate and
`
`
`
`
`
`
`
`
`
`an electrode 68A within pedestal 54 so as to excite the
`
`
`
`
`
`
`
`
`process gas mixture to form a plasma within the generally
`
`
`
`
`
`
`
`
`cylindrical region between the faceplate and pedestal. This
`
`
`
`
`
`
`
`is in contrast to an inductive coupling of RF powerinto the
`
`
`
`
`
`
`
`gas, as is provided in the chamber configuration shown in
`
`
`
`
`
`
`
`FIG.1A.In either a thermal or a plasmaprocess, substrate
`
`
`
`
`
`
`
`
`58 can be heated by a heating element 68B within pedestal
`54.
`
`
`
`
`
`
`
`
`
`
`[0050] According to the present invention, any or all of
`
`
`
`
`
`
`
`
`pedestal 54, heating element 68B gas distribution manifold
`
`
`
`
`
`
`
`
`56, and chamberliners 74 and 76 may be constructed from
`
`
`
`
`
`
`
`
`a ceramic material implanted with rare-earth ions according
`
`
`
`
`
`
`
`to the present invention. The embodiments of FIGS. 1A and
`
`
`
`
`
`
`
`1B are for exemplary purposes only, however. A person of
`
`
`
`
`
`
`
`
`
`
`
`skill in the art will recognize that other types of ceramic
`
`
`
`
`
`
`
`
`parts in these and other types of substrate processing cham-
`
`
`
`
`
`
`
`bers in which highly corrosive environments are contained
`
`
`
`
`
`
`
`
`(e.g., reactive ion etchers, electron cyclotron resonance
`
`
`
`
`
`
`
`
`plasma chambers,etc.) may benefit from the teaching of the
`
`
`present invention.
`
`
`
`
`II. Coating Formation
`
`
`
`
`
`
`
`[0052]
`In accordance with embodiments of the present
`
`
`
`
`
`invention, parent materials of components of semiconductor
`
`
`
`
`
`
`fabrication apparatuses are protected against corrosion by a
`
`
`
`
`
`
`
`
`surface coating containing a rare earth metal, the coating
`
`
`
`
`
`
`
`exhibiting low reactivity to a halogen gas environment at
`
`
`
`
`
`
`
`elevated temperatures. For purposes of this patent applica-
`
`
`
`
`
`
`tion, yttrtum is considered a rare earth metal.
`
`
`
`
`
`[0053] Surface coatings in accordance with embodiments
`
`
`
`
`
`
`
`of the present invention maintain adhesion to the parent
`
`
`
`
`
`
`material at high operating temperatures (up to 1000° C.).
`
`
`
`
`
`
`
`The surface coatings may include yttrium fluoride, yttrium
`
`
`
`
`
`oxides, yttrium-containing oxides of Aluminum (YAIO,,
`
`
`
`
`
`Y,3Al;0,5, Y,Al,0,), Erbium oxides, Neodymium oxide,
`and other rare earth oxides.
`
`
`
`
`
`
`
`
`
`
`
`[0054] The high operating temperatures of many plasma
`
`
`
`
`
`
`
`processes can create problemsarising from a lack of adhe-
`
`
`
`
`
`
`sion between a parent material and an overlying coating.
`
`
`
`
`
`
`Accordingly,it is useful to form an adhesion layer between
`
`
`
`
`
`the coating and parent material.
`
`
`
`
`
`
`
`
`[0055] This is illustrated in FIG. 2A, which is a cross-
`sectional view of coated member 215 in accordance with an
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`embodimentof the present invention. As shownin FIG. 2A,
`
`
`
`
`
`
`
`
`
`adhesion layer 212 overlies parent material 214, and coating
`
`
`
`
`
`
`
`
`
`216 is formed over adhesion layer 212. Parent material 214
`
`
`
`
`
`
`
`
`may comprise AIN, Al,O,, or some other material.
`In
`
`
`
`
`
`
`
`accordance with one embodimentof the present invention,
`
`
`
`
`
`
`
`rare earth-containing coating 216 may be deposited over
`
`
`
`
`
`
`
`adhesion layer 212 by sputtering techniques. Sputtering may
`
`
`
`
`
`
`
`take place in a particular ambient, for example by reactive
`
`
`
`
`
`
`
`sputtering of a target of the rare earth material in an oxygen
`
`
`
`
`
`
`ambient to create a rare earth oxide coating.
`
`
`
`
`
`
`
`[0056] Adhesion layer 212 may exhibit a coefficient of
`
`
`
`
`
`
`thermal expansion intermediate that of parent material 214
`
`
`
`
`
`
`
`
`and coating 216, such that coating 216 adheres to parent
`
`
`
`
`
`
`
`material 214 over a wide temperature range. The adhesion
`
`
`
`
`
`
`
`layer may be formed over the substrate by deposition prior
`
`
`
`
`to formation of the coating.
`
`
`
`
`
`
`
`[0057]
`In alternative embodiments in accordance with the
`
`
`
`
`
`
`
`present invention,
`the adhesion layer may be formed by
`
`
`
`
`
`
`
`
`accelerating rare earth ions toward the parent material at
`
`
`
`
`
`
`
`changed energies prior to formation of the surface coating.
`
`
`
`
`
`
`
`
`For example, adhesion layer 212 of structure 215 of FIG. 2A
`
`
`
`
`
`
`
`
`may result from ion-implantation, with reduction over time
`
`
`
`
`
`
`
`
`
`in the energy of implantation of rare earth metals into parent
`
`
`
`
`
`
`
`material 214 creating implanted adhesion layer 212.
`
`
`
`
`
`
`
`
`
`Implanted adhesion layer 212 may be graded, with the rare
`
`
`
`
`
`
`earth metal concentration gradient determined by duration of
`
`
`
`
`implantation at particular energy levels.
`
`
`
`
`
`
`[0058] Acceleration of rare-earth ions to a depth into the
`
`
`
`
`
`
`target parent material may be accomplished using a variety
`
`
`
`
`
`
`
`of techniques. In one implantation approach,rare earth ions
`
`
`
`
`
`
`
`are introduced into the parent material utilizing metal
`
`
`
`
`
`ion
`plasma
`immersion
`implantation
`and
`deposition
`
`
`
`
`
`
`(MEPIIID). FIG. 3 showsa simplified schematic view of the
`
`
`MEPIIID technique.
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Ex. 1037, Page 16
`
`Ex. 1037, Page 16
`
`

`

`
`
`US 2003/0029563 Al
`
`
`
`Feb. 13, 2003
`
`
`
`
`
`
`
`
`
`
`
`single or dual-source
`shown in FIG. 3,
`[0059] As
`
`
`
`
`
`
`
`
`MEPIIID source 300 is used to implant and deposit a layer
`
`
`
`
`
`
`
`
`
`of rare-earth ions over the component 300 being treated.
`
`
`
`
`
`
`
`
`With this technique, component 302 is inserted into plasma
`
`
`
`
`
`
`
`
`
`304 after plasma 304 has been deflected with magnetic filter
`
`
`
`
`
`
`
`
`304. Sheath edge 311 represents a concentrated plasma zone
`
`
`
`
`
`
`
`
`
`near biased target component 302, where mostreactions and
`
`
`
`rearrangements of materials occur.
`
`
`
`
`
`
`
`[0060] The treated component 302 is then subjected to
`
`
`
`
`
`
`
`implantation by biasing component 302 with a negative
`
`
`
`
`
`
`voltage utilizing electrode 307 in communication with
`
`
`
`
`
`
`
`
`powersupply 306. When target component302 is unbiased,
`
`
`
`
`
`
`
`
`
`it is subject to the initial deposition phase of the treatment
`
`
`
`
`
`
`
`process. When target component 302 is negatively biased
`
`
`
`
`
`
`
`
`
`(e.g., at -50 keV), ions 310 from plasma 304are accelerated
`
`
`
`
`
`
`
`
`toward target component302 at high velocities so that target
`
`
`
`
`
`
`component 302 is subjected to ion implantation to a depth
`
`
`
`
`
`
`
`
`
`into the material. The magnitude of the negative bias of the
`
`
`
`
`
`
`
`
`target material, and hence the energy of bombardment, is
`
`
`
`
`
`
`then reduced to produce a gradient of concentration of rare
`
`
`
`
`
`earth material to a depth in the material.
`
`
`
`
`
`
`[0061] A more detailed description of a single-source
`
`
`
`
`
`
`
`
`
`MEPIIID system is set forth in U.S. Pat. No. 5,476,691
`
`
`
`
`
`
`
`issued to Ian Brownet al., hereby incorporated by reference
`
`
`
`
`
`
`
`in its entirety.
`In a technique employing a dual-source
`
`
`
`
`
`
`
`MEPIIID implanter, the treatment process is similar except
`
`
`
`
`
`
`
`
`
`that plasmas from two separate plasma guns are brought
`
`
`
`
`
`
`together through independent magnetic channels, in order to
`
`
`
`
`
`
`
`deposit a thin film over the parent component.
`
`
`
`
`
`
`
`[0062] The MEPIIID approach to implantation of rare
`
`
`
`
`
`
`
`
`earth metals requires that the component be subject to an
`
`
`
`
`
`
`
`
`electrical bias. However, such biasing is not possible with
`
`
`
`
`
`
`
`
`
`parent materials that are poor conductors. This issue can be
`
`
`
`
`
`
`resolved if an electrode is embedded within the component,
`
`
`
`
`
`
`
`
`the embedded electrode capable of being biased during the
`
`
`
`
`
`
`
`
`
`implantation step. Such is the case for heaters and electro-
`static chucks.
`
`
`
`
`
`
`
`
`[0063] FIG. 4 is a graph that shows the concentration of
`
`
`
`
`
`
`
`rare-earth ions and aluminum nitride at various depths of an
`
`
`
`
`
`
`
`aluminum nitride componenttreated with a MEPIIID tech-
`
`
`
`
`
`
`
`
`nique. As can be seen in FIG. 4 the upper surface of the
`
`
`
`
`
`
`treated component comprises a layer M of rare-earth mate-
`
`
`
`
`
`
`
`
`
`rial formed from the deposition phases of the treatment
`
`
`
`
`
`
`
`process. Beneath layer M, the concentration of rare-earth
`
`
`
`
`
`
`
`
`
`ions decreases with depth until point N, where the concen-
`
`
`
`
`
`
`
`tration of rare-earth ions reaches background levels (essen-
`
`
`tially zero).
`
`
`
`
`
`
`
`
`[0064] Because of this profile of implanted material, a
`
`
`
`
`
`
`
`
`graded interface is obtained between the coated surface and
`
`
`
`
`
`
`
`
`
`the bulk of the parent material. An interface of this type
`
`
`
`
`
`
`
`provides a gradual transition of surface properties such as
`
`
`
`
`
`
`
`
`physical and chemical properties, and results in improved
`
`
`
`
`
`
`
`adhesion as compared to more abrupt, stepped profile dis-
`
`
`
`
`
`
`
`tributions. Such a graded interface also eliminates limita-
`
`
`
`
`
`
`tions of adhesion due to thermal mismatch—often a limiting
`
`
`
`
`
`
`
`
`factor of corrosion resistant coatings having an abrupt
`interface.
`
`
`
`
`
`
`
`
`[0065]
`In components having an abrupttransition between
`
`
`
`
`
`
`
`coating and parent material, the protective coating deposited
`
`
`
`
`
`
`over chamber materials may crack in response to environ-
`
`
`
`
`
`
`
`mental stresses. For example, during high temperature ther-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`mal cycles the temperature change during and/or between
`
`
`
`
`
`
`
`
`various cycles can be as high 700° C. for ceramic heater
`
`
`
`
`applications. Another example of an environmental stress
`
`
`
`
`
`
`
`that may induce cracking of a coating are the mechanical
`
`
`
`
`
`stresses associated with wafer handling.
`
`
`
`
`
`[0066] Once a crack in a coatingis initiated, in a corrosive
`
`
`
`
`
`
`environment aggressive and corrosive free radicals may
`
`
`
`
`
`
`
`
`penetrate the film coating and erode the underlying wall
`
`
`
`
`
`
`
`material. This penetration may cause film delamination and
`
`
`particulate contamination.
`
`
`
`
`
`[0067] By contrast, corrosion-resistant coatings in accor-
`
`
`
`
`
`
`
`dance with embodiments of the present invention may serve
`
`
`
`
`
`
`
`
`as a barrierto the diffusion of reactive species into the parent
`
`
`
`
`
`
`
`material. In this respect,
`implanted structures may have
`
`
`
`
`
`
`superior performanceandversatility as compared with struc-
`
`
`
`
`
`
`
`tures formed by plasma spray, CVD, laser ablation or PVD
`
`
`deposition techniques.
`
`
`
`
`
`[0068] FIG. 5 is a simplified cross-sectional view