# Patent

## Title
Plasma-resistant ceramics with controlled electrical resistivity

## Abstract

Specialty ceramic materials which resist corrosion/erosion under semiconductor processing conditions which employ a corrosive/erosive plasma. The corrosive plasma may be a halogen-containing plasma. The specialty ceramic materials have been modified to provide a controlled electrical resistivity which suppresses plasma arcing potential.

## Background
The present application is related to a series of applications which have common inventorship with the present application. All of the applications listed below relate to the use of a yttrium-oxide comprising ceramic to provide a plasma-resistant surface which is useful in semiconductor processing apparatus. The related applications include U.S. application Ser. No. 11/796,210, of Sun et al., filed Apr. 27, 2007, titled: “Method of Reducing The Erosion Rate Of Semiconductor Processing Apparatus Exposed To Halogen-Containing Plasmas”, which was abandoned in favor of U.S. application Ser. No. 12/660,068 titled: “Semiconductor Processing Apparatus Which Is Formed From Yttrium Oxide And Zirconium Oxide To Produce A Solid Solution Ceramic Apparatus”, which issued as U.S. Pat. No. 8,034,734 on Oct. 11, 2011; U.S. application Ser. No. 11/796,211, of Sun et al., filed Apr. 27, 2007, titled: “Method And Apparatus Which Reduce The Erosion Rate Of Surfaces Exposed To Halogen-Containing Plasmas”, which issued as U.S. Pat. No. 7,696,117 on Apr. 13, 2010; U.S. application Ser. No. 10/898,113 of Sun et al., filed Jul. 22, 2004, titled: “Clean Dense Yttrium Oxide Coating Protecting Semiconductor Apparatus”, which issued as U.S. Pat. No. 8,067,067 on Nov. 29, 2011; U.S. application Ser. No. 10/918,232 of Sun et al., filed Aug. 13, 2004, titled: “Gas Distribution Plate Fabricated From A Solid Yttrium Oxide-Comprising Substrate”, which issued as U.S. Pat. No. 7,479,304 on Jan. 20, 2009; and U.S. application Ser. No. 10/075,967 of Sun et al., filed Feb. 14, 2002, titled: “Yttrium Oxide Based Surface Coating For Semiconductor IC Processing Vacuum Chambers”, which issued as U.S. Pat. No. 6,776,873 on Aug. 17, 2004. Additional related applications filed, which are a divisional and a continuation application of above-listed applications, include: U.S. application Ser. No. 11/595,484 of Wang et al., filed Nov. 10, 2006, titled: “Cleaning Method Used In Removing Contaminants From The Surface Of An Oxide or Fluoride Comprising a Group III Metal”, which was a divisional application of U.S. application Ser. No. 10/898,113, and which was abandoned in favor of U.S. application Ser. No. 12/284,540, which issued as U.S. Pat. No. 8,016,948 on Sep. 13, 2009; and U.S. application Ser. No. 11/592,905 of Wang et al., filed Nov. 3, 2006, titled: “Cleaning Method Used In Removing Contaminants From A Solid Yttrium Oxide-Containing Substrate”, which is a continuation application of U.S. application Ser. No. 10/918,232, and which issued as U.S. Pat. No. 7,846,264 on Dec. 7, 2010. The subject matter of all of these patents and applications is hereby incorporated by reference.
BACKGROUND
1. Field
Embodiments of the present invention relate to a specialized yttrium oxide-comprising ceramic which is mainly comprised of solid solution ceramic which is highly resistant to plasmas of the kind which are present in semiconductor processing apparatus.
2. Background Art
This section describes background subject matter related to the disclosed embodiments of the present invention. There is no intention, either express or implied, that the background art discussed in this section legally constitutes prior art.
Corrosion (including erosion) resistance is a critical property for apparatus components and liners used in semiconductor processing chambers, where corrosive environments are present. Although corrosive plasmas are present in the majority of semiconductor processing environments, including plasma enhanced chemical vapor deposition (PECVD) and physical vapor deposition (PVD), the most corrosive plasma environments are those used for cleaning of processing apparatus and those used to etch semiconductor substrates. This is especially true where high-energy plasma is present and combined with chemical reactivity to act upon the surface of components present in the environment. The reduced chemical reactivity of an apparatus component surface or of a process chamber liner surface is an important property when corrosive gases, even in the absence of a plasma, are in contact with processing apparatus surfaces.
Process chamber liners and component apparatus present within the processing chambers used to fabricate electronic devices and micro-electro-mechanical systems (MEMS) are frequently constructed from aluminum and aluminum alloys. Surfaces of the process chamber and component apparatus (present within the chamber) are frequently anodized to provide a degree of protection from the corrosive environment. However, the integrity of the anodization layer may be deteriorated by impurities in the aluminum or aluminum alloy, so that corrosion begins to occur early, shortening the life span of the protective coating. The plasma resistance properties of aluminum oxide are not positive in comparison with some other ceramic materials. As a result, ceramic coatings of various compositions have been used in place of the aluminum oxide layer mentioned above; and, in some instances, have been used over the surface of the anodized layer to improve the protection of the underlying aluminum-based materials.
Yttrium oxide is a ceramic material which has shown considerable promise in the protection of aluminum and aluminum alloy surfaces which are exposed to halogen-containing plasmas of the kind used in the fabrication of semiconductor devices. An yttrium oxide coating has been used and applied over an anodized surface of a high purity aluminum alloy process chamber surface, or a process component surface, to produce excellent corrosion protection (e.g. U.S. Pat. No. 6,777,873 to Sun et al., mentioned above). The protective coating may be applied using a method such as spray coating, physical vapor deposition (PVD) or chemical vapor deposition (CVD) by way of example.
A film of Al2O3, or Al2O3 and Y2O3 has been formed on an inner wall surface of a processing chamber and on those exposed surfaces of the members within the chamber which require a high corrosion resistance and insulating property. In an exemplary application, a base material of the chamber may be a ceramic material (Al2O3, SiO2, AlN, etc.), aluminum, or stainless steel, or other metal or metal alloy, which has a sprayed film over the base material. The film may be made of a compound of a III-B element of the periodic table, such as Y2O3 The film may substantially comprise Al2O3 and Y2O3. A sprayed film of yttrium-aluminum-garnet (YAG) has also been mentioned. Examples of a sprayed film thickness range from 50 μm to 300 μm.
SUMMARY
Specialty sintered ceramic materials have been developed which resist corrosion under semiconductor processing conditions which employ a halogen-containing plasma. The specialty materials have been modified to have improved plasma resistance and tailored mechanical properties in comparison with the sintered ceramic materials previously used for semiconductor processing apparatus. The electrical properties of the sintered ceramic materials have been adjusted so that the electrical resistivity properties of the materials (which have an effect in a plasma processing chamber) meet the requirements of critical chamber components. These electrical resistivity property requirements were previously met only by materials which exhibited low plasma resistance properties. The present specialty materials (which offer various combinations of plasma resistance, mechanical properties, and electrical resistivity properties) are sufficiently similar to those of semiconductor processing apparatus previously used. One advantage of the similar electrical properties is that it is not necessary to change the process recipes or general processing conditions which are currently in use in semiconductor device fabrication.
The specialty sintered ceramic material used to fabricate semiconductor processing chamber components may be applied over an underlying material using thermal/flame spraying or plasma spraying, physical vapor deposition (such as sputtering from a target comprised of the specialty sintered ceramic material) or chemical vapor deposition, by way of example. In the alternative, the sintered ceramic material may be used to fabricate a solid component using a molding process, for example, when this is preferable to use of a coating.
The sintered ceramic materials of interest comprise yttrium oxide-based solid solutions. In one embodiment, the electrical resistivity of the sintered, yttrium oxide-comprising ceramic material is altered. In one exemplary embodiment technique, other oxides are added to the yttrium oxide, and the mixture is sintered. The positive ions of the other oxides have a different valence from the Y3+ ion, to form a Y vacancy, leading to a decrease of electrical resistivity. Examples of such other oxides include CeO2, TiO2, Zr02, HfO2, and Nb2O5, by way of example and not by way of limitation. In an alternative exemplary embodiment technique, other oxides are added to the yttrium oxide and the mixture is sintered. The positive ions of the other oxide show the same valence as the Y3+ ion, but possess a significantly different ion radius than the Y3+ ion. The precursor mixture is sintered in a reductive atmosphere. This results in an O vacancy, which also decreases electrical resistivity. Examples of oxides which show the same valence as the Y3+, ion, but possess a significantly different ion radius include Nd2O3, Sm2O3, Sc2O3, Yb2O3, Er2O3, Ho2O3 and Dy2O3, by way of example and not by way of limitation.
One of the major components in a semiconductor processing chamber which requires a lower resistivity than is typical for yttrium-comprising sintered ceramics is the electrostatic chuck. The electrostatic chuck designers recommend that the resistivity of the dielectric surface of the electrostatic chuck fall within a range from about 109 to 1011 Ω·cm under semiconductor processing conditions, to reduce the possibility of plasma arcing at the electrostatic chuck. This resistivity range is equivalent to a conductivity within a range from about 10−9 to 10−13 S/m. This is a considerably lower resistivity than bulk Si3N4, for example, which exhibits a conductivity of 10−13 S/m. For other corrosion resistant surfaces where plasma arcing might be a problem, such as lift pins, a resistivity in the range of that required for an electrostatic chuck is helpful. For corrosion resistant surfaces such as process chamber liners, the resistivity may be higher, possibly as high as or exceeding about 1014 Ω·cm and still be acceptable.
At least one solid solution forms the major molar % of sintered ceramic materials which are useful as electrically modified corrosion-resistant materials. When there are two oxides used to form a solid solution, these oxides typically comprise yttrium oxide in combination with another oxide, which is typically selected from the group consisting of zirconium oxide, cerium oxide, hafnium oxide, niobium oxide, and combinations thereof. Use of other oxides such as scandium oxide, neodymium oxide, samarium oxide, ytterbium oxide, erbium oxide, and cerium oxide (and other lanthanide series element oxides) is considered to be acceptable in some instances.
When there are more than two oxides used to form the one or more solid solutions, these oxides typically comprise yttrium oxide, zirconium oxide, and at least one other oxide, which is typically selected from the group consisting of hafnium oxide, scandium oxide, neodymium oxide, niobium oxide, samarium oxide, ytterbium oxide, erbium oxide, cerium oxide, and combinations thereof. The use of other lanthanide series elements is also possible in particular instances. When the sintered ceramics comprise multi solid solution phases, typically there are two phases or three phases. In addition to the at least one solid solution-phase, there may be other phases within the sintered ceramic which are compounds or elemental metals.
By way of example, and not by way or limitation, with respect to sintered ceramics which make use of two precursor oxides, experiments have confirmed that a sintered ceramic comprising a solid solution, where yttrium oxide is present over a range from about 40 molar % to less than 100 molar %, and zirconium oxide is present over a range from more than 0 molar % to about 60 molar %, produces a sintered oxide having a resistivity which is in the range from about 107 to about 1015 Ω·cm at room temperature. Resistivity over the same range is expected to be obtained from a combination of precursor oxides where yttrium oxide is present over a range from more than 0 molar % to less than 100 molar %, and cerium oxide is present over a range from greater than 0 molar % up to less than 10 molar %. Resistivity over a range from about 109 to about 1011 Ω·cm is also expected to be obtained from a combination of precursor oxides where yttrium oxide is present over a range from more than 0 molar % to less than 100mole %, and hafnium oxide is present over a range from more than 0 molar % up to less than 100 molar %. Sintered ceramic exhibiting a resistivity over a range of about 109 to about 1011 Ω·cm is also expected to be obtained from a combination of precursor oxides where yttrium oxide is present over a range from about 48 molar % to less than 100 mole %, and niobium oxide is present over a range from greater than 0% up to about 52 molar %.
By way of example, and not by way of limitation, with respect to sintered ceramics which make use of more than two precursor oxides, in one embodiment, a sintered ceramic will exhibit a resistivity over a range of about 107 to about 1015 Ω·cm when the sintered ceramic comprises a solid solution, and where the sintered ceramic material is formed from oxides where: yttrium oxide is present over a range from about 40 molar % to less than 100 molar %; zirconium oxide is present over a range from more than 0 molar % to about 50 molar %; and, scandium oxide is present over a range from more than about 0 molar % up to less than 100 molar %.
In another embodiment, a sintered ceramic will exhibit an electrical resistivity over a range of about 107 to about 1015 Ω·cm when the sintered ceramic comprises a solid solution, and the sintered ceramic material is fabricated from oxides where: yttrium oxide is present over a range from about 40 molar % to less than 10 molar %; zirconium oxide is present over a range from more than 0 molar % to about 50 molar %, and hafnium oxide is present over a range from more than about 0 molar % up to less than 100 molar %.
In yet another embodiment, a sintered ceramic will exhibit a resistivity over a range of about 107 to about 1015 Ω·cm when the sintered ceramic comprises a solid solution, and the sintered ceramic material is fabricated from oxides where: yttrium oxide is present over a range from about 40 molar % to less than 100 molar %; zirconium oxide is present over a range from more than 0 molar % to about 45 molar %; and, niobium oxide is present over a range from more than about 0 molar % up to about 80 molar %.
In one embodiment, the sintered ceramic material contains three phases, which include: a first phase solid solution comprising Y2O3—ZrO2—Nb2O5 which makes up from about 60 molar % to about 90 molar % of the sintered ceramic material; a second phase of Y3NbO7 which makes up from about 5 molar % to about 30 molar % of the sintered ceramic material; and, a third phase of Nb in elemental form, which makes up from about 1 molar % to about 10 molar % of the sintered ceramic material.
In another embodiment of the sintered ceramic material which contains three phases, yttrium oxide is present over a range from about 60 molar % to about 75 molar %; zirconium oxide is present over a range from about 15 molar % to about 25 molar %, and niobium oxide is present over a range from about 5 molar % to about 15 molar %.
In sintered ceramic test specimens formed from a Y2O3—ZrO2-MxOy material of the kind described above, in embodiments where M is scandium, hafnium, niobium, or neodymium, an erosion rate was demonstrated which was 0.16 μm/hour or less, after exposure for 76 hours to a CF4/CHF3 plasma. A similar erosion rate is expected when M is cerium, samarium, erbium, or another lanthanide series element. The plasma was formed in an Enabler for Trench Etch plasma processing chamber available from Applied Materials, Inc. The plasma source power was up to 2000 W, the process chamber pressure was 10-500 mTorr, and the substrate temperature was 40° C. This erosion rate of 0.16 μm/hour or less is equivalent to the erosion rate of pure Y2O3. Thus, the erosion rate of the sintered ceramics has been unaffected by the modification of the sintered ceramic to provide a lower resistivity sintered ceramic.
While the ceramic materials described above were sintered ceramics formed from oxides using sintering techniques known in the art, in other embodiments, the starting material compositions listed above may be used to form a ceramic coating over the surface of a variety of metal and ceramic substrates, including, but not limited to, aluminum, aluminum alloy, stainless steel, alumina, aluminum nitride and quartz, using a coating technique. Such coating techniques include plasma spraying, thermal/flame spraying; physical vapor deposition from a sputtering target which is formed by sintering the oxides; or, chemical vapor deposition, by way of example and not by way of limitation.



BRIEF DESCRIPTION OF THE DRAWINGS
To assist in the understanding of the above recited embodiments, a more particular description of specific embodiments described above may be had by reference to the appended drawings. It is to be noted, however, that the appended drawings illustrate only a portion of the typical embodiments, and are not therefore considered to be limiting in scope of the invention which is described herein. The invention includes other equally effective embodiments.
FIG. 1 is a graph 100 illustrating the electrical resistivity, as a function of temperature, for a variety of materials, where the applied voltage was 1000 V in an air environment.
FIG. 2 is a phase diagram 200 of Y2O3—ZrO2—Al2O3. This phase diagram shows, among other compositions, the composition of a specialized material, identified herein as an area “A” on the phase diagram, for reference purposes. The type “A” ceramic material is a ceramic composition which has demonstrated excellent resistance to erosion by halogen plasmas.
FIG. 3 is a phase diagram 300 of Y2O3—ZrO2—Nb2O5. This phase diagram shows, among other compositions, the composition of a specialized material, identified herein as an area “B” on the phase diagram, for reference purposes. The type “B” ceramic material is a ceramic composition which not only resists erosion by halogen plasmas, but which also exhibits a controlled, lower electrical resistivity than the type “A” ceramic material, for example.
FIG. 4 is a graph 400 illustrating electrical resistivity, as a function of applied voltage, for a variety of materials, where the measurement was made at room temperature (about 27° C.) in an air environment.
FIG. 5 is a bar chart 500 which shows the average exemplary erosion rate, normalized relative to that for pure yttrium oxide, for a variety of sintered ceramic materials which were exposed to a plasma generated from CF4 and CHF3 source gases.



DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
As a preface to the detailed description, it should be noted that, as used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents, unless the context clearly dictates otherwise.
When the word “about” is used herein, this is intended to mean that the nominal value presented is precise within ±10%.
Described herein are specialized ceramic materials which are developed to resist corrosion under semiconductor device processing conditions which employ a halogen-containing plasma. In certain embodiments, the specialty materials have been modified to have a reduced electrical resistivity when compared with similar ceramic materials which were developed previously to provide plasma erosion resistance. The reduced electrical resistivity is helpful in reducing the possibility of plasma arcing at various components within a semiconductor processing chamber, most notably upon a surface of an electrostatic chuck or a substrate lift pin, where plasma arcing is more of a problem, for example and not by way of limitation. In the past the component, or at least the surface of the component was fabricated from aluminum nitride or aluminum oxide, which might be doped to provide electrical properties. While this material provided the desired electrical properties, the corrosion/erosion rate was relatively rapid, limiting the useful lifetime of the particular component, and requiring more down time for repairs and replacement of component parts.
Further, the electrical properties of the various materials used as process chamber liners and functional components within a plasma processing semiconductor apparatus affect the behavior of the plasma. Changes in the behavior of the plasma affect the plasma processing characteristics, and when the effect is substantial, it is necessary to change other process variables to accommodate the change in the plasma behavior. Rather than rework processing variables for device fabrication, it is more practical to develop erosion resistant ceramic materials which have acceptable electrical properties. Only a portion of the ceramic materials which exhibit acceptable plasma corrosion/erosion characteristics can be modified to control electrical resistivity properties within the desired range useful for a component in contact with plasmas. One skilled in the art and having read the present description will be able to be relatively certain of success when selecting combinations of oxides to form the ceramic materials.
For reasons of convenience, the development of acceptable halogen plasma corrosion/erosion-resistant ceramic materials having the desired electrical properties was carried out by making use of sintered ceramics. The sintered ceramics were produced by techniques well known in the art. In other embodiments, acceptable halogen plasma corrosion/erosion-resistant ceramic materials of the same general composition may be applied as a coating over an underlying material, such as aluminum or aluminum alloy, for example, using thermal/flame spraying or plasma spraying. In the alternative, a sintered ceramic material may be used to fabricate a target which may be used to apply the ceramic material by physical vapor deposition over the underlying material, particularly when the apparatus over which the protective ceramic material is to be applied is large, such as a process chamber liner.
As previously discussed, the sintered ceramic materials of interest comprise yttrium oxide. The resistivity of the sintered, yttrium-comprising ceramic material may be altered. In one exemplary technique, at least one other oxide is added to the yttrium oxide and the mixture is sintered. The positive ions of the at least one other oxide have a different valence from the Y3+ ion, to form a Y vacancy, leading to a decrease of electrical resistivity. Examples of such oxides include CeO2, TiO2, ZrO2, HfO2, and Nb2O5, by way of example and not by way of limitation. In another exemplary technique, the at least one other oxide is added to yttrium oxide, and the mixture is sintered in a reductive atmosphere; however, the positive ions of the at least one other oxide show the same valence as the Y3+ ion, but possess a significantly different ion radius than the Y3+ ion. This results in an O vacancy, which also decreases electrical resistivity. Examples of oxides which show the same valence as the Y3+ ion, but possess a significantly different ion radius include Nd2O3, Sm2O3, Sc2O3, Yb2O3, Er2O3, Ho2O3 and Dy2O3, by way of example and not by way of limitation.
A number of exemplary sintered ceramic materials have been investigated to date, and the TABLE below provides an illustration of a portion of the sintered ceramic materials which were created and evaluated. The evaluation of these materials is discussed subsequently.
EXAMPLES














TABLE








Precursor









Weight
Melting
Sintering



Precursor
Precursor
Parts/100
Point
Temp.
Phase
Density


Sample #
Molar %
Weight %
Y2O3
(° C.)
(° C.)
Comp.
(g/cm3)







1
Y2O3: 75.0
Y2O3: 77.82
Y2O3: 100.00
2800
>1800
c-ss
5.607



HfO2: 20.0
HfO2: 19.35
HfO2: 24.86


single



ZrO2: 5.0
ZrO2: 2.83
ZrO2: 3.64


phase**


2
Y2O3: 60.0
Y2O3: 72.18
Y2O3: 100.00
2360
>1800
c-ss
4.936



Sc2O3: 20.0
Sc2O3: 14.69
Sc2O3: 20.36


single



ZrO2: 20.0
ZrO2: 13.13
ZrO2: 18.19


phase**


3
Y2O3: 60.0
Y2O3: 59.58
Y2O3: 100.00
N/A*
>1800
c-ss
5.555



Nd2O3: 20.0
Nd2O3: 29.58
Nd2O3: 49.66


single



ZrO2: 20.0
ZrO2: 10.84
ZrO2: 18.19


phase**


4
Y2O3: 70.0
Y2O3: 75.53
Y2O3: 100.00
N/A*
>1800
c-ss**
5.331



Nb2O5: 10.0
Nb2O5: 12.7
Nb2O5: 16.82


Y3NbO



ZrO2: 20.0
ZrO2: 11.77
ZrO2: 15.59


and Nb





*N/A = not available


**c-ss means cubic yttria type solid solution.






Example One
FIG. 1 shows a graph 100 illustrating electrical resistivity of a variety of ceramic materials, including the Type A and Type B materials made according to exemplary embodiments of the invention. The resistivity is shown on axis 104, as a function of temperature, which is shown on axis 102. The resistivity was measured at 1000 V in an air environment, using standard test conditions in accordance with ASTM D 1829-66 or JIS C2141.
Curve 106 shown in FIG. 1 is representative of the Nb2O5-comprising sintered ceramic material which is described as Sample #4 in the Table. With respect to sintered ceramic material comprising Nb2O5, acceptable electrical resistivity values are expected to be obtained for additional compositions as well, as illustrated by the phase diagram shown in FIG. 3. The sintered ceramic material contains three phases, which include a first phase solid solution comprising Y2O3—ZrO2—Nb2O5 which may make up about 60 molar % to about 90 molar % of the sintered ceramic material; a second phase of Y3NbO7 which may make up from about 5 molar % to about 30 molar % of the sintered ceramic material; and, a third phase of Nb in elemental form, which may make up from about 1 molar % to about 10 molar % of the sintered ceramic material. This material is particularly useful when the resistivity needs to be low to prevent arcing. The resistivity is lower than about 1011 Ω·cm at room temperature and about 108 Ω·cm at 200° C., and may exhibit a resistivity in the range of 109 Ω·cm at typical semiconductor processing conditions.
One embodiment of the Nb2O5-comprising sintered ceramic material illustrated in FIG. 1 is referred to as Nb2O5—ZrO2—Y2O3. With reference to FIG. 3, one area of the phase diagram has been labeled as “B”. This designation indicates that the solid solution composition of a sintered ceramic material comprises Y2O3 at a concentration ranging from about 55 molar % to about 80 molar %, ZrO2 at a concentration ranging from about 5 molar % to about 25 molar %, and an additive such as Nb2O5, HfO2, Nd2O3, or Sc2O3 at a concentration ranging from about 5 molar % to about 25 molar %.
Example Two
Curve 108 shown in FIG. 1 is representative of the HfO2-comprising sintered ceramic material, made in accordance with the present invention, which is also described as Sample #1 in the Table. This ceramic material exhibits a higher resistivity than the Nb2O5-comprising material, but is useful for fabricating semiconductor processing apparatus components where arcing is less critical than with respect to an electrostatic chuck or a substrate lift pin.
Example Three
Curve 110 shown in FIG. 1 is representative of the Sc2O3-comprising sintered ceramic material, made in accordance with the present invention, which is also described as Sample 2 in the Table. Again, this material may be used in applications where the resistivity requirement is 1011 Ω·cm.
Example Four (Comparative Example)
Curve 112 shown in FIG. 1 is representative of the Y2O3—ZrO2—Al2O3 material which is illustrated in the FIG. 2 phase diagram . This material is described for purposes of a comparative example only with respect to the controlled resistivity ceramic materials. This sintered ceramic material comprises a solid solution which is formed from Y2O3 and ZrO2, and a compound which is formed from Y2O3 and Al2O3 oxides. A typical sintered ceramic material is formed from Y2O3 at a concentration ranging from about 60 molar % to about 65 molar %; ZrO2 at a concentration ranging from about 20 molar % to about 25 molar %; and, Al2O3 at a concentration ranging from about 10 molar % to about 15 molar %. One embodiment of a sintered ceramic material, which is illustrated by area “A” in the phase diagram in FIG. 2, and which is represented by the graph for Y2O3—ZrO2—Al2O3 shown in FIG. 1, contains: about 60 molar % solid solution with a cubic yttria type crystal structure, where c-Y2O3 is a solvent, with Zr2O3 solute; about 2 molar % solid solution with a fluorite type crystal structure, where ZrO2 is a solvent, with Y2O3 solute; and about 38 molar % YAM (Y4Al2O9) compound.
Example Five (Comparative Example)
Curve 114 of FIG. 1 is representative of the Nd2O3-comprising sintered ceramic material which is described as Sample #3 in the Table. This material failed to meet the requirements which are necessary to prevent arcing, and is considered to be a comparative example which is not part of the unique ceramic materials which make up the invention.
Example Six (Comparative Example)
Curve 116 of FIG. 1 is representative of the electrical resistivity characteristics observed for a sintered ceramic of pure Y2O3. This material is also a comparative example, which is useful as a baseline, since a number of semiconductor apparatus components have been fabricated from pure Y2O3. A comparison of the resistivity of the pure Y2O3 shows the very significant improvement in terms of electrical resistivity which is achieved by the present invention.
Also shown in FIG. 1 are curves 120, which represents a doped aluminum nitride of the kind commonly used to fabricate an electrostatic chuck, and 122 which represents a second doped aluminum nitride which is also used to fabricate an electrostatic chuck and other semiconductor processing apparatus which require a low electrical resistivity.
Example Seven
FIG. 4 is a graph 400 which illustrates the electrical resistivity, as a function of the voltage applied during the resistivity testing, for a number of sintered ceramic test specimens. The resistivity is shown on axis 404, with the voltage shown on axis 402. The test temperature is room temperature (about 27° C.). The purpose of this graph is to illustrate the differences in resistivity between the corrosion-resistant ceramic embodiments of the present invention which have been controlled to reduce resistivity and the currently used doped aluminum nitride ceramics. While the doped aluminum nitride ceramics have a somewhat lower resistivity, their corrosion rate is at least 2 times higher than that of the yttrium oxide-comprising ceramics which have been modified to reduce resistivity.
In particular, Curve 422 of FIG. 4 represents doped aluminum nitride ceramic of the kind currently used to fabricate an electrostatic chuck. Curve 420 represents another doped aluminum nitride ceramic which is used to fabricate an electrostatic chuck and other low resistivity components.
Curve 406 of FIG. 4 is representative of the Nb2O5-comprising sintered ceramic material which is described as Sample #4 in the Table. This yttrium-oxide comprising material which has been modified to reduce resistivity exhibits a resistivity which is very close to that of the doped aluminum nitride identified as AlN-1. Yet, the corrosion rate of the doped aluminum nitride is more than 10 times faster than the corrosion rate of the yttrium-oxide comprising material illustrated by curve 406, as is shown by the bar chart 500 in FIG. 5.
Curve 408 in FIG. 4 is representative of the HfO2-comprising sintered ceramic material which is described as Sample #1 in the Table. This ceramic material exhibits a higher resistivity than the Nb2O5-comprising material, and at room temperature exhibits a resistivity which is outside of the recommended range for components where plasma arcing is more likely to occur. However, at 200° C., a temperature which is present during some semiconductor processing, the resistivity falls within an acceptable range, as illustrated by Curve 108 in FIG. 1.
Curve 410 of FIG. 4 is representative of the Sc2O3-comprising sintered ceramic material which is described as Sample 2 in the Table. Again, this material may be used in applications where the resistivity requirement is 1011 Ω·cm, when the processing temperature is 200° C.
For comparative purposes (with respect to a controlled electrical resistivity ceramic containing a yttria-comprising solid solution), Curve 412 of FIG. 4 shows a ceramic type “A” material comprising Y2O3, ZrO2, and Al2O3 which is illustrated in FIG. 2. One embodiment of such a type “A” material, which is shown in FIG. 1, contains about 60 molar % cubic yttria type structure with c-Y2O3 as a solvent and with Zr2O3 solute; about 2 molar % fluorite-type structure solid solution with ZrO2 as a solvent and with Y2O3 solute; and, about 38 molar % YAM (Y4Al2O9) compound. While the Type A HPM material exhibits acceptable corrosion-resistant properties and commendable mechanical properties, the electrical resistivity is considerably higher that the desired range maximum 1011 Ω·cm. This is the case even at 200° C., as illustrated by Curve 112 in FIG. 1. This material is not included among the embodiments for the electrical resistivity modified corrosion resistant ceramics.
For comparative purposes, Curve 414 of FIG. 4 shows the Nd2O3-comprising sintered ceramic material which is described as Sample #3 in the Table. This material failed to meet the requirements which are necessary to prevent arcing, and is considered to be a comparative example which is not part of the unique ceramic materials which make up the invention.
For comparative purposes, Curve 416 of FIG. 4 shows the electrical resistivity characteristics observed for a sintered ceramic of pure Y2O3. This material is also a comparative example, which is useful as a baseline, since a number of semiconductor apparatus components have been fabricated from pure Y2O3. A comparison of the resistivity of the pure Y2O3 shows the very significant improvement in terms of electrical resistivity which is achieved by the present invention.
Example Eight
FIG. 5 illustrates a bar chart 500 which shows the average erosion rate in μm/hr of a variety of sintered ceramic materials exposed to a plasma. The plasma was generated from CF4 and CHF3 source gases. The plasma processing chamber was an Enabler for Trench Etch available from Applied Materials, Inc. The plasma source power was up to 2000 W, the process chamber pressure was 10-500 mTorr, and the substrate temperature was about 40 ° C., for a time period of 76 hours. The axis 502 shows a variety of materials which were tested for erosion resistance. The test specimen identified by a description Y2O3-10 ZrO2, represents a sintered solid solution ceramic test specimen which was formed by sintering 100 parts by weight Y2O3 in combination with 10 parts by weight of ZrO2. The test specimens identified as containing Nb2O5-, or HfO2 -, or Nd2O3-, or Sc2O3- represent the TABLE compositions which are recited as containing each of those materials. A comparison of the erosion rates as shown on axis 504 shows that the erosion rates of the resistivity modified, yttrium oxide-comprising sintered ceramic materials are essentially the same as the erosion rate for pure yttrium oxide. Further, the erosion rates of the resistivity modified, yttrium oxide-comprising sintered ceramics are substantially better than the erosion rate of Al2O3, AlN, ZrO2, Quartz, W/ZrC, B4C and SiC, other ceramic materials which have been used to provide a halogen plasma corrosion-resistant materials for semiconductor processing chamber liners and on semiconductor processing apparatus interior components.
Based on the results obtained during the experimentation which provided the examples described above, and data from other reference sources, calculations have been made which provide estimates of the effect of UV radiation in plasma leakage current. UV radiation in a plasma environment (of the kind used in semiconductor processing) does not have an effect on leakage current of electrical resistivity-modified yttrium oxide-comprising sintered ceramic materials.
An investigation of the effect of 193 nm UV irradiation (which is employed in some semiconductor processing operations) on the leakage current in the Nb2O5- Type B sintered ceramic material and the HfO2-Type B sintered ceramic material has indicated that the electrical performance of these materials should not be affected by such UV irradiation.
The ceramic-comprising articles which are useful as semiconductor processing apparatus which is in contact with a plasma include a lid, a liner, a nozzle, a gas distribution plate, a shower head, an electrostatic chuck component, a shadow frame, a substrate-holding frame, a processing kit, and a chamber liner, by way of example and not by way of limitation.
The above described exemplary embodiments are not intended to limit the scope of the present invention, as one skilled in the art can, in view of the present disclosure, expand such embodiments to correspond with the subject matter of the invention claimed below.

## Claims

1. A ceramic-comprising article having a surface comprising at least one solid solution, wherein said article is useful in semiconductor plasma processing chambers which require both corrosive plasma erosion resistance and an electrical resistivity which reduces the possibility of arcing, wherein said solid solution is formed from precursor oxides where yttrium oxide is present at a concentration ranging from about 55 molar % to about 80 molar %, zirconium oxide is present at a concentration ranging from about 5 molar % to about 25 molar %, and wherein hafnium oxide, niobium oxide, or a combination thereof is present at a concentration ranging from about 5 molar % to about 25 molar %.

2. A ceramic-comprising article in accordance with claim 1, said ceramic-comprising article having a surface comprising a three phase sintered ceramic material which includes a first phase of solid solution comprising Y2O3—ZrO2—Nb2O5 which makes up from about 60 molar % to about 90 molar % of the sintered ceramic material; a second phase of Y3NbO7 which makes up from about 5 molar % to about 30 molar % of the sintered ceramic material; and, a third phase of Nb in elemental form, which makes up from about 1 molar % to about 10 molar % of the sintered ceramic material.

3. A ceramic-comprising article in accordance with claim 1 or claim 2, wherein said article is in the form of an electrostatic chuck, an electrostatic chuck component, or a substrate lift pin, which requires an electrical resistivity in the range of about 107 to 1015 Ω·cm at a temperature ranging from about 350° C. to room temperature.

4. A ceramic-comprising article in accordance with claim 1 or claim 2, wherein said article is in the form of an internal component or a liner used in the interior of a semiconductor processing chamber.

5. A ceramic-comprising article in accordance with claim 1 or claim 2, wherein said article is a solid sintered ceramic article.

6. A ceramic-comprising article in accordance with claim 1 or claim 2, wherein said article is selected from the group consisting of an electrostatic chuck, a lid, a liner, a nozzle, a gas distribution plate, a shower head, an electrostatic chuck component,a shadow frame, a substrate holding frame, a processing kit, and a chamber liner.

7. A ceramic-comprising article in accordance with claim 1 or claim 2, wherein said surface is a coating of said three phase sintered ceramic material formed over a substrate which substrate comprises a material selected from the group consisting of aluminum, aluminum alloy, stainless steel, alumina, aluminum nitride, and quartz.

8. A ceramic-comprising article in accordance with claim 7, wherein said coating is present over at least a portion of said substrate and was applied using a technique selected from the group consisting of plasma spraying, thermal/flame spraying, physical vapor deposition, and chemical vapor deposition.