# Patent

## Title
Tantalum PVD component producing methods

## Abstract

A method for producing a tantalum PVD component includes a minimum of three stages, each of which include a deformation step followed by a high-temperature anneal. The deformation occurs in air and at a component temperature less than or equal to 750° F. in at least one of the minimum of three stages. The anneal occurs at a component temperature of at least 2200° F. in at least the first two of the minimum of three stages. The tantalum component exhibits a uniform texture that is predominately {111}<uvw>. As an alternative, the deformation may occur at a component temperature of from 200° F. to 750° F. in at least the last stage of the minimum of three stages. The anneal may occur at a component temperature of from 1500° F. to 2800° F. in at least three of the minimum of three stages.

## Background
RELATED APPLICATION DATA
This application is a continuation-in-part of U.S. patent application Ser. No. 09/999,095, filed Oct. 30, 2001, now U.S. Pat. No. 7,101,447, which is a divisional application of U.S. patent application Ser. No. 09/497,079, filed Feb. 2, 2000, now U.S. Pat. No. 6,331,233, the entire subject matter of which is herein incorporated by reference.


TECHNICAL FIELD
This invention relates to the processing of high-purity tantalum to produce a physical vapor deposition (PVD) component with a microstructure that is desirable for uniform deposition. In particular, the invention relates to the manufacture of high-purity tantalum with a mean grain size of less than 100 μm and a uniform, predominately (111)<uvw> crystallographic texture throughout the component thickness.
BACKGROUND OF THE INVENTION
Tantalum is currently used extensively in the electronics industry, which employs tantalum in the manufacture of highly effective electronic capacitors. Its use is mainly attributed to the strong and stable dielectric properties of the oxide film on the anodized metal. Both wrought thin foils and powders are used to manufacture bulk capacitors. In addition, thin film capacitors for microcircuit applications are formed by anodization of tantalum films, which are normally produced by sputtering. Tantalum is also sputtered in an Ar—N2 ambient to form an ultra thin TaN layer which is used as a diffusion barrier between a Cu layer and a silicon substrate in new generation chips to ensure that the cross section of the interconnects can make use of the high conductivity properties of Cu. It is reported that the microstructure and stoichiometry of the TaN film are, unlike TiN, relatively insensitive to the deposition conditions. Therefore, TaN is considered a much better diffusion barrier than TiN for chip manufacture using copper as metallization material. For these thin film applications in the microelectronics industry, high-purity tantalum sputtering targets are needed.
The typical tantalum target manufacture process includes electron-beam (EB) melting ingot, forging/rolling ingot into billet, surface machining billet, cutting billet into pieces, forging and rolling the pieces into blanks, annealing blanks, final finishing, and bonding to backing plates. The texture in tantalum plate is very dependent on processing mechanisms and temperatures. According to Clark et al. in the publication entitled “Effect of Processing Variables on Texture and Texture Gradients in Tantalum” (Metallurgical Transactions A, September 1991), the texture expected to develop in cold-rolled and annealed body-centered cubic (bcc) metals and alloys consists of orientations centered about the ideal orientations, {001}<110>, {112}<110>, {111}<110>, and {111}<112>. Generally, conventionally processed tantalum is forged or rolled from ingot to final thickness, with only one (1) or no intermediate annealing stages. A final anneal is usually applied to the plate simply to recrystallize the material. The direction of the deformation influences the strengths of resulting annealed textures but generally little attention is given to the resulting distribution of textures. In conventionally processed tantalum, significant texture variation exists in the cross-section of the plate, as described by Clark et al., “Influence of Transverse Rolling on the Microstructural and Texture Development in Pure Tantalum,” Metallurgical Transactions, Vol. 23A, August 1992, p. 2183-2191m; Raabe et al., “Texture and Microstructure of Rolled and Annealed Tantalum,” Materials Science and Technology, Vol. 10, April 1994, p. 299-305; and Michaluk et al., “Methodologies for Determining the Global Texture of Tantalum Plate Using X-ray Diffraction,” Tantalum, The Minerals, Metal & Materials Society, 1996, p. 123-131.
Typically the above mentioned textures exist in stratified bands through the thickness of the rolled plate, or form a gradient of one texture on the surface usually {100}<uvw>, with a gradual transition to a different texture at the centerline of the plate, usually {111}<uvw>. Wright et al., “Effect of Annealing Temperature on the Texture of Rolled Tantalum and Tantalum-10 wt. % Tungsten” (Proceedings of the 2nd International Conference on Tungsten and Refractory Metals, pg 501-508, 1994). Another cause of texture variation through the target thickness is the non-uniformity of the deformation processes used to form the plate. Texture non-uniformity results in variable sputter deposition rates and sputter surface irregularities, which in turn is believed to be a source of micro-arcing.
Micro-arcing is believed to believed to be the principle cause of particle generation and is thus undesirable in the semiconductor industry. FIG. 1 shows the sputter surface of a mixed-texture tantalum target made by conventional processing methods. The sputter surface reveals regions of two different crystallographic textures; dark areas are {100}<uvw>, lighter areas {111}<uvw>. The type of pattern illustrated in FIG. 1 is believed to contribute to sputter film nonuniformities because of the different sputter rates associated with each texture.
FIG. 2 shows severe textural banding in the cross-section of a sputtered tantalum target manufactured according to conventional processes. “Textural banding,” refers to a localized concentration of one texture in the cross section strung out over several grains in a matrix of another texture. In tantalum, it is typically {100}<uvw> textures in a matrix of the more prominent {111}<uvw> textures. For example, a series of grains with the same {100}<uvw> texture in a matrix of {111}<uvw> that are aligned in an elongated manner over several grains is considered a banded textural feature. Using Electron Backscatter Diffraction, EBSD, imaging the texture in small, localized areas can be determined accurately.
In FIG. 2, it can be clearly seen that areas of {100}<uvw> type textures sputter at a greater rate than {111}<uvw> type textures. Thus, any textural non-uniformity at the target surface can produce surface “ridges,” which have an increased likelihood of causing micro-arcing.
SUMMARY OF THE INVENTION
In one aspect of the invention, a method for producing a tantalum PVD component includes a minimum of three stages, each of which include a deformation step followed by a high-temperature anneal. The deformation occurs in air and at a component temperature less than or equal to 750° F. in at least one of the minimum of three stages. The anneal occurs at a component temperature of at least 2200° F. in at least the first two of the minimum of three stages. By way of example, the annealing may occur in an inert atmosphere. The tantalum component exhibits a uniform texture that is predominately {111}<uvw> throughout a thickness of the component.
In another aspect of the invention, a method for producing a tantalum PVD component comprising a minimum of three stages, each of which include a deformation step followed by a high-temperature anneal. The deformation occurs in air and at a component temperature of from 200° F. to 750° F. in at least the last stage or the third stage of the minimum of three stages. The anneal occurs at a component temperature of from 1500° F. to 2800° F. in at least three of the minimum of three stages. By way of example, the annealing may occur in an inert atmosphere. The tantalum component exhibits a uniform texture that is predominately {111}<uvw> throughout a thickness of the component.



BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are described below with reference to the following accompanying drawings.
FIG. 1 is a photograph of a used high purity tantalum sputtering target with a non-uniform texture throughout the target thickness.
FIG. 2 is a cross-sectional EBSD image of a conventionally processed, severely banded sputtered tantalum target.
FIG. 3 is a schematic of a process according to one aspect of the invention.
FIG. 4 is a cross-sectional EBSD image of a conventionally processed (Process 2 summarized in Table 1), severely banded high-purity tantalum sputtering target.
FIG. 5 is a cross-sectional EBSD image of a conventionally processed (Process 3 summarized in Table 1), high-purity tantalum sputtering target.
FIG. 6 is a cross-sectional EBSD image of a high-purity tantalum sputtering target manufactured by Process 4 summarized in Table 1.
FIG. 7 is cross-sectional EBSD image of a high-purity tantalum sputtering target manufactured by Process 7 summarized in Table 1.
FIG. 8 is a cross-sectional EBSD image of a high-purity tantalum sputtering target manufactured by a process according to one aspect of the invention (Process 12 summarized in Table 1).
FIG. 9(a) is a photograph of an experimental sputtering target manufactured by a conventional method (Process 4).
FIG. 9(b) is a photograph of an experimental sputtering target manufactured by a process according to one aspect of the invention (Process 12).



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention there is provided a processing route for producing high purity tantalum PVD components with a mean fine grain size of less than 100 microns and uniform crystallographic texture throughout the component thickness. As known to those of ordinary skill, PVD includes, but is not limited to sputtering.
The method includes forging, rolling and annealing high-purity, vacuum-melted tantalum ingots in such a way as to eliminate remnant as-cast grain structure, and produce a homogeneous fine-grain size (mean<100 μm) microstructure with a uniform, predominately {111}<uvw> texture throughout the thickness of the target. Significant sputtering problems have been reported when the texture of the target is not uniform throughout the target thickness. Sputtering rates and film deposition rates can change as a function of target crystallographic texture. This variable sputter rate across a target surface causes film thickness uniformity problems and also produces unwanted surface topography in the form of “ridging,” which in turn is believed to cause micro-arcing.
In one aspect, the invention uses a series of deformation techniques, with a minimum of three (3) intermediate, high-temperature inert-atmosphere anneals, preferably under vacuum conditions, to produce a fine-grain size (mean<100 μm) tantalum targets with a uniform, predominately {111}<uvw> texture throughout the target thickness that, until now, was unseen in the industry. “Uniform texture throughout the target thickness” refers to a homogeneous distribution of textural components with no visible banding at a resolution of 20× from the target surface to at least mid-thickness. “Inert” refers to an atmosphere that is non-reactive with the tantalum-containing mass.
Experiments associated with this invention also revealed that, by controlling the annealing temperature, the most desirable texture for collimated sputtering, the (111) texture, can be generated. The (111) texture is the only texture that has one of the close-packed directions aligned normal to the target surface. This direction is a dominant emission direction and is, therefore, the texture required for collimated sputtering.
The high-purity tantalum material of the present invention is preferably 3N5 (99.95%) pure and contains less than 500 ppm total metallic impurities, excluding gases. The methods of chemical analysis used to derive the chemical descriptions set forth herein are the methods known as glow discharge mass spectroscopy (GDMS) for metallic elements and LECO gas analyzer for non-metallic elements.
In the context of the present document, the term “PVD components” includes, but is not limited to, PVD targets. Deposition may occur from other components in a deposition chamber such as coils, pins, etc. and, thus, a desire may exist for PVD components other than targets to contain the materials and/or be formed by the methods described herein.
Electron beam (EB), Vacuum Arc Melted (VAR), or other vacuum melted tantalum ingots are deformed perpendicular to the ingot centerline to break up the as-cast grain microstructure. This deformation can be forging, rolling, or extrusion whereby significant cross-sectional area or thickness reduction takes place. The reduction in cross-sectional area may be greater than a reduction ratio of 3:1 (cross-sectional area of ingot to cross-sectional area of the forged billet), or equivalent to no less than about 40% strain reduction from starting thickness to final thickness. The forged billet may then be annealed in an inert atmosphere, preferably vacuum, at a high temperature greater than about 1500° F. or, advantageously, greater than 2200° F. to achieve a recrystallized microstructure. As a practical matter, anneal temperature may be from about 1500° F. to about 2800° F. or, advantageously, from 2000° F. to 2500° F. to avoid processing too hot. A particularly advantageous anneal temperature that achieves excellent results is from 2200° F. to 2400° F.
The resulting billet/plate is then deformed no less than an additional 35%, preferably 45-65%, of its thickness and subjected to a second high-temperature inert atmosphere anneal, within the same temperature ranges described for the first anneal, to achieve a recrystallized microstructure. However, the particular temperature or temperature range selected may be different from the first anneal. The process of the present invention includes an additional deformation step with a strain greater than or equal to 60% followed by a final inert-atmosphere anneal within the same temperature ranges described for the first anneal to recrystallize the microstructure to the desired fine grain size. Since grain size control is desired in the final anneal, the most advantageous temperature is from about 1750° F. to about 1800° F.
FIG. 3 is a schematic of the invented process. The deformation directions amenable to achieving the desired results may be used, according to the knowledge of those of ordinary skill. The process of this invention preferably utilizes no less than three deformation steps and no less than three inert-atmosphere anneal steps from ingot to final target plate thickness in order to achieve the desired results. Three or more deformation and intermediate inert-atmosphere, high-temperature annealing stages are more likely to eliminate grain size and textural banding while maintaining a mean grain size of less than 100 microns than would less than 3 deformation and annealing stages.
It may be additionally advantageous to incorporate warm deformation techniques. For example, the deformation may occur at a component temperature less than or equal to 750° F. in at least one of the stages. A temperature of from 200° F. to 750° F. may provide a greater advantage. Warm deformation in at least the last two stages, potentially three stages, of a minimum of three stages may also provide a greater advantage. Primarily, the advantage results from the yield strength of tantalum during deformation being reduced with increasing temperature. The lowered yield strength allows a greater thickness reduction, which may provide a more uniform stress distribution during deformation.
At higher temperatures, such as those used in the annealing techniques described herein, oxidation of tantalum might become a concern. Accordingly, annealing may occur in an inert atmosphere. However, deforming at 750° F. or less does not create a significant risk of tantalum oxidation and may occur in air. Deforming at 750° F. or less in air thus allows greater flexibility in thickness reduction and selection of a processing atmosphere without a significant risk of oxidation. As a practical matter, warm deformation allows the use of larger work pieces since greater thickness reductions, compared to cold deformation techniques, are possible enroute to producing a PVD component of a specified thickness. Using warm deformation, similar or improved results compared to those demonstrated in Processes 8 through 12 of Table 1 may be obtained for larger work pieces and/or may provide more uniform strain distributions.
EXAMPLE 1
Twelve high-purity tantalum ingots were processed according to conventional methods or according to aspects of the invention. The parameters for each experiment and the corresponding grain size and texture results are summarized in Table 1. Texture uniformity was measured by cutting samples from the target and analyzing them using an EBSD system on a scanning electron microscope (SEM). The mapped area was 7 mm×7 mm and was measured from the target surface to at least the plate mid-thickness. The lighter areas depict {111}<uvw> textures and the darker areas depict {100}<uvw> textures.
The ingots processed by conventional methods (Processes 1 through 7) exhibited a banded microstructure in both grain size and texture. FIGS. 4, 5, 6 and 7 illustrate the extent of this banding. The ingots manufactured by the invented process (Processes 8 through 12) have a strong {111}<uvw> texture with a random distribution of {100}<uvw> texture. FIG. 8, which represents a product according to aspects of the invention, shows a high degree of textural uniformity throughout the target cross-section, with no banding.
Although the experimental data show the grain size results to be less than about 50 μm it is expected that a grain size of less than 100 μm will produce similar sputtering results, so long as the texture is uniform throughout the target thickness.
EXAMPLE 2
Sputter trials were conducted on a conventional high-purity tantalum target and a target processed according to this invention in order to compare the sputtering characteristics. FIG. 9(a) and FIG. 9(b) are photographs of the used conventional and invented targets, respectively. The conventional target exhibits extensive surface roughness which is associated with non-uniform sputtering. This surface “ridging” in turn increases the likelihood of micro-arcing and sputter film non-uniformity. In contrast, the target processed according to aspects of the invention exhibits a smooth evenly-sputtered surface.
In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed include preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents.




















TABLE 1














Pro-
Pro-
Pro-
Pro-
Pro-



Pro-
Pro-
Pro-
Pro-
Pro-
Pro-
Pro-
cess 8
cess 9
cess 10
cess 11
cess 12



cess 1
cess 2
cess 3
cess 4
cess 5
cess 6
cess 7
Inven-
Inven-
Inven-
Inven-
Inven-



Conven
Conven
Conven
Conven
Conven
Conven
Conven
tion
tion
tion
tion
tion




























Ingot Melting Process
VAR
E-Beam
E-Beam
E-Beam
E-Beam
E-Beam
E-Beam
E-Beam
E-Beam
E-Beam
E-Beam
E-Beam


Purity
4N
4N
3N5
3N5
4N
3N8
3N8
3N8
3N8
4N
3N8
3N8


Ingot break-up (Stage
None
None
>40%
>40%
None
>40%
>40%
>40%
>40%
>40%
>40%
>40%


I deformation)


High-temperature,
No
No
No
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes


inert-atmosphere


anneal?


Stage 2 deformation
>40%
>40%
>40%
>40%
>40%
>40%
>40%
>40%
>40%
>40%
>40%
>40%


High-temperature,
Yes
Yes
Yes
Yes
Yes
No
No
Yes
Yes
Yes
Yes
Yes


inert-atmosphere


anneal?


Stage 3 deformation
—
—
—
—
>60%
>60%
>60%
>60%
>60%
>60%
>60%
>60%


High-temperature,
—
—
—
—
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes


inert-atmosphere


anneal?


Number of anneals
 1
 1
 1
 2
 2
 2
 2
 3
 3
 3
 3
 3


Mean grain size (μm)
Banded
Heavy
35 μm
55 μm
Banded
30 μm
37 μm
35 μm
51 μm
45 μm
39 μm
22 μm



50-250
Banding


50-200



μm
100-250


μm




μm


Texture Description
Mixed
Mixed
Mixed
(111)
Mixed
Mixed
(100) at
Strong
Strong
Strong
Strong
Strong



(111) &
(111) &
(111) &
with
(111) &
(111) &
surface
(111)
(111)
(111)
(111)
(111)



(100),
(100),
(100),
banded
(100),
(100),
and
with
with
with
with
with



banded
banded
banded
(100)
banded
Extreme
(111) at
random
random
random
random
random








banded
center-
distri-
distri-
distri-
distri-
distri-









line
bution
bution
bution
bution
bution










of (100)
of (100)
of (100)
of (100)
of (100)


Texture uniformity
Very
Very
Poor
Poor
Poor
Very
Poor
Good
Excel-
Excel-
Excel-
Excel-


through thickness
Poor
Poor



Poor


lent
lent
lent
lent

## Claims

1. A method for producing a tantalum PVD component comprising a minimum of three stages, each of which include a deformation step followed by an inert atmosphere high-temperature anneal, the deformation occurring in air and at a component temperature less than or equal to 750° F. in at least one of the minimum of three stages, the anneal occurring at a component temperature of at least 2200° F. in at least the first two of the minimum of three stages, and the tantalum component exhibiting a mean grain size of less than about 100 microns and a uniform texture that is predominately {111}<uvw> throughout a thickness of the component.

2. The method of claim 1 wherein the anneal occurs at a component temperature of from 2200° F. to 2400° F. in the first two of the minimum of three stages.

3. The method of claim 1 wherein the anneal occurs at a component temperature of from about 1750° F. to about 1800° F. in the last stage of the minimum of three stages.

4. A method for producing a tantalum PVD component comprising a minimum of three stages, each of which include a deformation step followed by an inert atmosphere high-temperature anneal, the deformation occurring in air and at a component temperature of from 200° F. to 750° F. in at least the last stage of the minimum of three stages, the anneal occurring at a component temperature of from 1500° F. to 2800° F. in at least three of the minimum of three stages, and the tantalum component exhibiting a mean grain size of less than about 100 microns and a uniform texture that is predominately {111}<uvw> throughout a thickness of the component.

5. The method of claim 4 wherein the mean grain size is less then about 50 microns and the method further comprises forming a thin film tantalum-containing capacitor by:
sputtering the tantalum component to form a thin film; and
forming a thin film tantalum-containing capacitor using the sputtered tantalum.

6. The method of claim 4 further comprising forming a capacitor by:
forming a first capacitor electrode;
sputtering the tantalum component to form a tantalum layer over the capacitor electrode;
anodizing the sputtered tantalum to form a capacitor dielectric; and
forming a second capacitor electrode over the capacitor dielectric.

7. The method of claim 4 further comprising forming a capacitor by:
forming a first capacitor electrode;
collimated sputtering of the tantalum component to form a tantalum layer over the capacitor electrode;
forming a capacitor dielectric containing the sputtered tantalum; and
forming a second capacitor electrode over the capacitor dielectric.

8. The method of claim 4 wherein the high-temperature anneal occurs at a temperature of 2000° F. to 2500° F. in at least the first two of the minimum of three stages.

9. The method of claim 4 wherein the high-temperature anneal occurs at a temperature of 2200° F. to 2400° F. in at least the first two of the minimum of three stages.

10. The method of claim 4 wherein the high-temperature anneal occurs at a temperature of about 1750° F. to about 1800° F. in the last stage of the minimum of three stages.

11. The method of claim 4 wherein the high-temperature anneal occurs at different temperatures in at least three of the minimum of three stages.

12. The method of claim 4 wherein the deformation occurs at a component temperature of from 200° F. to 750° F. in at least the last two stages of the minimum of three stages.

13. A method for producing a tantalum PVD component, comprising:
providing an initial tantalum-containing mass;
first deforming the initial mass to form a first deformed mass, the first deforming including reducing a thickness of the initial mass;
first annealing the first deformed mass at a first temperature of at least 2200° F.;
second deforming the first deformed mass to form a second deformed mass, the second deforming including reducing a thickness of the first deformed mass;
second annealing the second deformed mass at a second temperature of at least 2200° F.;
third deforming the second deformed mass to form a third deformed mass, the third deforming including reducing a thickness of the second deformed mass; and
third annealing the third deformed mass at a third temperature of at least about 1500° F., one or more of the first, second, or third deforming steps occurring in air with the respective tantalum-containing mass at a temperature less than or equal to 750° F., and the tantalum component exhibiting a uniform texture that is predominately {111}<uvw> throughout a thickness of the component.

14. The method of claim 13 wherein the tantalum component exhibits a mean grain size of less than about 100 microns.

15. The method of claim 13 wherein the first and second temperatures are from 2200° F. to 2400° F.

16. The method of claim 13 wherein the third temperature is from about 1750° F. to about 1800° F.

17. A method for producing a tantalum PVD component, comprising:
providing an initial tantalum-containing mass;
first deforming the initial mass to form a first deformed mass, the first deforming including reducing a thickness of the initial mass;
first annealing the first deformed mass at a first temperature of from about 1500° F. to about 2800° F.;
second deforming the first deformed mass to form a second deformed mass, the second deforming including reducing a thickness of the first deformed mass;
second annealing the second deformed mass at a second temperature of from about 1500° F. to about 2800° F.;
third deforming the second deformed mass to form a third deformed mass, the third deforming including reducing a thickness of the second deformed mass and occurring in air with the second deformed mass at a temperature of from 200° F. to 750° F.; and
third annealing the third deformed mass at a third temperature of from about 1500° F. to about 2800° F., the tantalum component exhibiting a uniform texture that is predominately {111}<uvw> throughout a thickness of the component.

18. The method of claim 17 wherein the first and second temperatures are from 2000° F. to 2500° F.

19. The method of claim 17 wherein the first and second temperatures are from 2200° F. to 2400° F.

20. The method of claim 17 wherein the third temperature is from about 1750° F. to about 1800° F.

21. The method of claim 17 wherein the first, second and third temperatures are different from one another.

22. The method of claim 17 wherein the second deforming occurs in air with the first deformed mass at a temperature of from 200° F. to 750° F.

23. The method of claim 17 wherein the first deforming comprises reducing the thickness of the mass by at least about 40%.

24. The method of claim 17 wherein the second deforming comprises reducing the thickness of the first deformed mass by at least about 35%.

25. The method of claim 17 wherein the third deforming comprises reducing a thickness of the second deformed mass by at least about 60%.

26. The method of claim 17 wherein the initial tantalum-containing mass is in the form of an ingot and wherein the third deformed mass has a thickness corresponding to a plate thickness of the tantalum component formed from the ingot.

27. The method of claim 17 wherein at least one of the first, second, and third annealing comprises vacuum annealing.

28. The method of claim 17 wherein the mass is exposed to a first ambient during the first annealing, is exposed to a second ambient during the second annealing, and is exposed to a third ambient during the third annealing; the first, second and third ambients consisting of components which are inert relative to reaction with the tantalum-containing mass.