# Patent

## Title
Methods of forming capacitors

## Abstract

A method of forming a capacitor includes depositing a dielectric metal oxide layer of a first phase to a thickness no greater than 75 Angstroms over an inner conductive capacitor electrode material. The first phase dielectric metal oxide layer has a k of at least 15. Conductive RuO2 is deposited over and into physical contact with the dielectric metal oxide layer. Then, the RuO2 and the dielectric metal oxide layer are annealed at a temperature below 500° C. The RuO2 in physical contact with the dielectric metal oxide during the annealing facilitates a change of the dielectric metal oxide layer from the first phase to a second crystalline phase having a higher k than the first phase. The annealed dielectric metal oxide layer is incorporated into a capacitor dielectric region of a capacitor construction. Other implementations are disclosed.

## Background
RELATED PATENT DATA
This patent resulted from a continuation application of U.S. patent application Ser. No. 12/496,890 which was filed Jul. 7, 2009 that is hereby incorporated by reference.


TECHNICAL FIELD
Embodiments disclosed herein pertain to methods of forming capacitors.
BACKGROUND
Capacitors are commonly-used electrical components in semiconductor integrated circuitry, for example memory circuitry such as DRAM circuitry. A typical capacitor is comprised of two conductive electrodes separated by a non-conducting capacitor dielectric region. As integrated circuit density increases, there is a continuing challenge to maintain sufficiently high storage capacitance despite decreasing capacitor area. One way of increasing cell capacitance is through cell structure techniques. Such techniques include 3-dimensional cell capacitors such as trenched and stack capacitors. Other ways of increasing cell capacitance include the development and utilization of new materials for one or both of the capacitor electrodes and the capacitor dielectric region.
One way of maximizing capacitance is to use one or more dielectrics for the capacitor dielectric region which have a very high dielectric constant k. Certain dielectric metal oxides can be used for such purposes. Dielectric metal oxides may occur in multiple different amorphous and crystalline phases, with each phase having a different dielectric constant. It has been discovered in some instances that deposition of dielectric metal oxide layers at and below 75 Angstroms may require subsequent high temperature annealing well in excess of 500° C. to achieve desired highest-k phases for such different materials. Unfortunately, exposure of the substrate to such high temperatures can result in damage of other circuitry components and materials. Accordingly, it would be desirable to develop techniques that enable fabrication of capacitors having high k dielectrics that do not require exposure of substrates to high temperatures after deposition of the capacitor dielectric layers.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic sectional view of a substrate in process in accordance with an embodiment of the invention.
FIG. 2 is a view of the FIG. 1 substrate at a processing step subsequent to that shown by FIG. 1.
FIG. 3 is a view of the FIG. 2 substrate at a processing step subsequent to that shown by FIG. 2.
FIG. 4 is a view of the FIG. 3 substrate at a processing step subsequent to that shown by FIG. 3.
FIG. 5 is a diagrammatic sectional view of a substrate in process in accordance with an embodiment of the invention.
FIG. 6 is a view of the FIG. 5 substrate at a processing step subsequent to that shown by FIG. 5.
FIG. 7 is a diagrammatic sectional view of a substrate in process in accordance with an embodiment of the invention.
FIG. 8 is a view of the FIG. 7 substrate at a processing step subsequent to that shown by FIG. 7.
FIG. 9 is a view of the FIG. 8 substrate at a processing step subsequent to that shown by FIG. 8.
FIG. 10 is a view of the FIG. 9 substrate at a processing step subsequent to that shown by FIG. 9.
FIG. 11 is a diagrammatic sectional view of a substrate in process in accordance with an embodiment of the invention.
FIG. 12 is a view of the FIG. 11 substrate at a processing step subsequent to that shown by FIG. 11.
FIG. 13 is a diagrammatic sectional view of a substrate in process in accordance with an embodiment of the invention.
FIG. 14 is a diagrammatic sectional view of a substrate in process in accordance with an embodiment of the invention.



DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS
First embodiment methods of forming capacitors are described with reference to FIGS. 1-4. Referring to FIG. 1, a substrate fragment is indicated generally with reference numeral 10, and may comprise a semiconductor substrate. In the context of this document, the term “semiconductor substrate” or “semiconductive substrate” is defined to mean any construction comprising semiconductive material, including, but not limited to, bulk semiconductive materials such as a semiconductive wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure, including, but not limited to, the semiconductive substrates described above. Example substrate 10 is depicted as comprising a base material or substrate 12 outwardly of which a capacitor will be formed. Substrate 12 will likely comprise multiple different composition materials and layers which may be insulative, conductive, and/or semiconductive.
An inner conductive capacitor electrode material 14 has been deposited over substrate 12. Such may be homogenous or non-homogenous, with conductively doped semiconductive materials and one or more metals being examples. In the context of this document, a “metal” encompasses elemental form metals, alloys of elemental metals, and one or more conductive metal compounds. Examples include conductively doped silicon, titanium, tungsten, conductive metal nitrides, platinum, ruthenium, and conductive metal oxides. An example thickness range for inner conductive capacitor electrode material 14 is from 50 Angstroms to 300 Angstroms.
Referring to FIG. 2, a dielectric metal oxide layer 16 of a first phase has been deposited to a thickness no greater than 75 Angstroms over inner conductive capacitor electrode material 14. First phase dielectric metal oxide layer 16 has a dielectric constant “k” of at least 15. Dielectric layer 16 may or may not be placed into direct physical touching contact with inner conductive capacitor electrode material 14. Accordingly, one or more different capacitor dielectric materials may be provided intermediate first phase dielectric metal oxide layer 16 and conductive capacitor electrode material 14, for example as indicated by the three vertical dots between layers 14 and 16. Regardless, in one embodiment, thickness of dielectric metal oxide layer 16 is no greater than 60 Angstroms, and in one embodiment is no greater than 50 Angstroms.
The first phase of dielectric metal oxide layer 16 may be amorphous or crystalline. Regardless, the metal oxide of layer 16 may only contain a single metal element, or may comprise multiple metal elements. Specific high k dielectric example materials for layer 16 having a k of at least 15 include at least one of ZrO2, TiO2, Ta2O5, HfO2, and Nb2O5.
Dielectric metal oxide layer 16 may be deposited by any existing or yet-to-be developed manner, with one or a combination of chemical vapor deposition and atomic layer deposition being examples. Any suitable precursors may be used, for example metal halides and metalorganics as metal-containing precursors, and compounds comprising oxygen materials may be used as oxygen-containing precursors. For example for ZrO2, example chemical vapor deposition or atomic layer deposition precursors for zirconium include zirconium tetrachloride, tris(dimethyl-amido) (cyclopentadienyl)zirconium, tris(dimethyl-amido)(methyl-cyclopentadienyl)zirconium, tris(dimethyl-amido)(ethyl-cyclopentadienyl)zirconium, tetraethyl methyl amido zirconium, and tetrakis dimethyl amido zirconium. Example oxygen-containing precursors include O2, O3 and H2O. Mixtures of two or more of the various precursors may also of course be used. By way of examples only, deposition conditions include a substrate temperature from 250° C. to 350° C. and subatmospheric chamber pressure from 0.5 Torr to 5 Torr.
Still referring to FIG. 2, conductive RuO2 18 has been deposited over and into physical contact with dielectric metal oxide layer 16. Such may be of any amorphous or crystalline phase as-deposited. In one embodiment, thickness of RuO2 18 is at least 50 Angstroms. In one embodiment, thickness of RuO2 is from 75 Angstroms to 300 Angstroms, with a more specific ideal embodiment being from 100 Angstroms to 150 Angstroms.
RuO2 18 may be deposited by any existing or yet-to-be developed manner, with one or both of the atomic layer deposition and chemical vapor deposition being examples. Example temperature, pressure and oxygen-containing precursors may be the same as those described above for deposition of dielectric metal oxide layer 16. Example ruthenium-containing precursors include bis(cyclopentadienyl)ruthenium, bis(ethyl-cyclopentadienyl)ruthenium, bis(dimethyl-pentadienyl)ruthenium, tris(tetra-methyl-heptanedionate)ruthenium, (dimethyl-pentadienyl)(ethyl-cyclopentadienyl)ruthenium, (methyl-cyclopentadienyl)(pyrrolyl)ruthenium, (tetraethylmethylamido)ruthenium, and (tetrakisdimethylamido)ruthenium.
Referring to FIG. 3, RuO2 18 and dielectric metal oxide layer 16 have been annealed at a temperature below 500° C. The RuO2 18 in physical contact with the dielectric metal oxide of layer 16 during the annealing has facilitated or imparted a change of dielectric metal oxide layer 16 from the first phase to a second crystalline phase which has a higher k than the first phase. Such is exemplified in FIG. 3 by showing dielectric metal oxide layer 16 as being stippled in comparison to FIG. 2. In one embodiment, the annealing is conducted at a temperature of at least 200° C., and in one embodiment at a temperature of no greater than 400° C. Pressure may be atmospheric, subatmospheric, or greater than atmospheric, and the ambient during the annealing may be inert or not inert.
In one embodiment wherein the RuO2 as-deposited is amorphous, such will become crystalline as a result of the annealing. In one embodiment, the second crystalline phase is tetragonal and the RuO2 as-deposited is of a phase other than tetragonal. The annealing in such embodiment changes the phase of the RuO2 to tetragonal.
It has been discovered that provision of a RuO2 layer in direct physical touching contact with a dielectric metal oxide layer having a k of at least 15, and where the metal oxide layer has a thickness no greater than 75 Angstroms, can significantly reduce the time and temperature to which the metal oxide layer must be exposed to achieve a desired highest-k crystalline state. For example, ZrO2 deposited to a thickness of 70 Angstroms or less deposits into one of an amorphous, monoclinic, or cubic phase as opposed to a highest-k and desired tetragonal phase. In the absence of direct physical touching contact with a RuO2 layer, the ZrO2 layer as-deposited must be subjected to a temperature of at least 600° C. for at least 5 minutes to achieve complete transformation to the tetragonal phase. Provision of a RuO2 layer in direct physical touching contact therewith enables temperatures below 500° C. to be used.
As specific examples, a 150 Angstrom thick RuO2 layer received over a 50 Angstrom thick layer of ZrO2 will transform such ZrO2 layer to the tetragonal phase in any ambient or any pressure with an annealing temperature of 250° C. in 5 minutes or less. If the same as-deposited ZrO2 layer of 50 Angstroms is contacted by a 100 Angstrom thick layer of RuO2, exposure to a temperature of 400° C. for 5 minutes or less will result in transformation to the desired tetragonal phase.
The second crystalline phase may be tetragonal, hexagonal, or other, for example depending upon the composition of the dielectric metal oxide. For example, for TiO2, HFO2, and ZrO2, the desired highest-k phase is tetragonal. With respect to Ta2O5 and Nb2O5, the highest-k crystalline phase is hexagonal.
The above stated act of annealing may be conducted as a dedicated anneal for the specific and/or sole purpose of transformation to the higher k second crystalline phase. Alternately, such annealing may inherently result from subsequent processing of the substrate for one or more other purposes. For example, deposition of additional layers at temperatures greater than room temperature and below 500° C. may result in or constitute the stated above act of annealing. For example, if an outer capacitor electrode material of one or both of conductively doped polysilicon and titanium nitride were deposited, such may be conducted at a temperature and for a sufficient period of time to provide the stated act of annealing.
Regardless, annealed dielectric metal oxide layer 16 will be incorporated into a capacitor dielectric region of a capacitor construction. For example, FIG. 3 depicts annealed dielectric metal oxide layer 16 as comprising a portion of a capacitor dielectric region 20 of a capacitor construction 22. Capacitor dielectric region 20 may only be constituted by annealed dielectric metal oxide layer 16, or may include one or more additional materials between annealed dielectric metal oxide layer 16 and inner conductive capacitor electrode material 14. Regardless, capacitor construction 22 in FIG. 3 is depicted as comprising capacitor dielectric region 20, inner conductive capacitor electrode material 14, and an outer conductive capacitor electrode 24 which comprises the annealed conductive RuO2 18. One or more additional conductive materials may be added to comprise a portion of outer conductive capacitor electrode 24. For example as shown in FIG. 4, conductive material 26 has been deposited over RuO2 18 to comprise a portion of outer conductive capacitor electrode 24. Conductive material 26 may be homogenous or non-homogenous, comprising one or more different composition conductive layers and materials. In one embodiment, material 26 may comprise or consist essentially of additional RuO2.
In some embodiments, RuO2 may not be desired in a finished capacitor construction to comprise a portion of the outer capacitor electrode. Alternately if RuO2 is desired to be a composition of an outer capacitor electrode, it may be desired that such not be in direct physical touching contact with the capacitor dielectric region in the finished capacitor construction. Accordingly, after the above stated act of annealing, at least some or perhaps all of the annealed RuO2 may be etched from the substrate. For example, FIGS. 5 and 6 depict an alternate example method of forming a capacitor with respect to a substrate fragment 10a. Like numerals from the first described embodiments have been used where appropriate, with some construction differences being indicated with the suffix “a” or with different numerals. FIG. 5 depicts processing immediately subsequent to that depicted by FIG. 3, and wherein all of RuO2 18 (not shown) has been etched from the substrate. Only some of RuO2 18 may be etched away, although FIG. 5 shows all of such being etched away. An example etching chemistry that will etch RuO2 selectively relative to other dielectric metal oxide materials comprises O3, for example a mixture of O2 and O3 where O3 is from 18 percent to 22 percent by volume of such mixture.
Referring to FIG. 6, conductive material 26 has been deposited over annealed dielectric metal oxide layer 16, thereby forming outer conductive capacitor electrode 24a. 
Example additional embodiments of methods of forming capacitors are next described with reference to FIGS. 7-10 with respect to a substrate fragment 10b. Like numerals from the above described embodiments have been used where appropriate, with some construction differences being indicated with the suffix “b” or with different numerals. Referring to FIG. 7, inner conductive capacitor electrode material 14b has been deposited over substrate 12. Material 14b may be the same as that of material 14 and will have some outermost portion 30 thereof which comprises RuO2. Outermost portion 30 may be of any suitable thickness, with example thickness ranges provided above for RuO2 material 18 being examples.
Referring to FIG. 8, dielectric metal oxide layer 16 of a first phase has been deposited to a thickness no greater than 75 Angstroms over and into physical contact with the RuO2 30 of inner conductive capacitor electrode material 14b. 
Referring to FIG. 9, RuO2 30 and dielectric metal oxide layer 16 have been annealed at a temperature below 500° C. The RuO2 30 in physical contact with dielectric metal oxide of layer 16 during the annealing has facilitated or imparted a change of the dielectric metal oxide layer 16 from the first phase to a second crystalline phase having a higher k than the first phase. Example processing is as described above with respect to the first-described embodiments.
The annealed dielectric metal oxide layer 16 of second crystalline phase of higher k may be incorporated into some of all of a capacitor dielectric region of a capacitor construction comprising inner and outer capacitor electrodes. Accordingly, outer conductive capacitor electrode material will be deposited over the dielectric metal oxide layer. Intervening materials or layers may be received between the outer conductive capacitor electrode material and the dielectric metal oxide layer 16 which was subjected to the phase transforming annealing. Alternately, the dielectric metal oxide layer subjected to the phase transforming annealing may be in direct physical touching contact with the outer conductive capacitor electrode material.
FIG. 10 depicts a capacitor construction 22b comprising inner conductive capacitor electrode material 14b, outer conductive capacitor electrode 24b, and having a capacitor dielectric region 20b received there-between. Annealed dielectric metal oxide layer 16 comprises a portion of capacitor dielectric region 20b, and one or more other materials or layers may be received thereover as indicated by the three vertically arranged dots. Alternately, outer conductive capacitor electrode 24b may be in direct physical contact with annealed dielectric metal oxide 16. Further and regardless, the above stated act of annealing in the embodiments of FIGS. 7-10 may be conducted as a dedicated anneal, and regardless the annealing may occur before, during or after deposition of outer conductive capacitor electrode 24b. 
RuO2 may be etched appreciably using O3. Accordingly in one embodiment wherein a dielectric metal oxide layer is deposited over RuO2, it may be desired in such a deposition to at least start the deposition using an oxygen-containing precursor which is void of O3, for example to avoid etching of RuO2. In one embodiment after the inner conductive capacitor electrode material is covered with dielectric metal oxide using an oxygen-containing precursor which is void of O3, depositing of the dielectric metal oxide layer may be continued using O3.
It may be desirable to provide RuO2 in physical contact both above and below a dielectric metal oxide layer when the above annealing is conducted. FIGS. 11 and 12 show an example such embodiment with respect to a substrate fragment 10c. Like numerals from the above-described embodiments have been used where appropriate, with some construction differences being indicated with the suffix “c” or with different numerals. FIG. 11 depicts processing as may occur immediately subsequent to that shown by FIG. 8. Specifically, conductive RuO2 18 has been deposited over and into physical contact with dielectric metal oxide layer 16.
Referring to FIG. 12, RuO2 18 and 30 and dielectric metal oxide layer 16 have been annealed as described above to form the second crystalline phase having a higher k than the first crystalline phase. Some or all of RuO2 18 may be etched away from the substrate, for example as described above in connection with respect to the embodiment of FIGS. 5 and 6. Alternately or additionally, RuO2 18 may comprise some or all of an outer conductive capacitor electrode material.
FIG. 13 depicts an additional alternate embodiment substrate fragment 10d to that shown in the processing described with reference to FIGS. 11 and 12. Like numerals from the above-described embodiments have been used where appropriate, with some construction differences being indicated with the suffix “d” or with different numerals. In FIG. 13, an inner conductive capacitor electrode material 14b has been deposited which comprises RuO2 30 as an outermost portion thereof. A first dielectric metal oxide layer 16 of a first phase has been deposited to a thickness no greater than 75 Angstroms over and into physical contact with RuO2 30.
One or more additional or different composition dielectric layers are provided over first dielectric metal oxide layer 16. For example in the FIG. 13 embodiment, at least a second dielectric layer 40 has been deposited over first dielectric metal oxide layer 16, wherein second dielectric layer 40 is of different composition from that of first dielectric metal oxide layer 16. Ideally, second dielectric layer 40 is a high k dielectric having a k of at least 15, and regardless may or may not comprise a dielectric metal oxide. One or more additional dielectric layers may be provided between second dielectric layer 40 and first dielectric metal oxide layer 16, for example as indicated by the three vertical dots between layers 16 and 40.
A third dielectric metal oxide layer 50 is deposited to a thickness no greater than 75 Angstroms over second dielectric layer 40. Intervening dielectric layers may be provided between layers 50 and 40 as indicated by the three vertical dots between layers 50 and 40. Regardless, third dielectric metal oxide layer 50 is of different composition from that of second dielectric layer 40, and has a k of at least 15. First and second dielectric metal oxide layers 16 and 50 may be of the same composition or may be of different compositions. Further, such may be of the same or different thicknesses.
Conductive RuO2 18 has been deposited over and into physical contact with third dielectric metal oxide layer 50. Thereafter, the substrate is annealed at a temperature below 500° C. The RuO2 30 in physical contact with first dielectric metal oxide layer 16 during the annealing facilitates or imparts a change of first dielectric metal oxide layer 16 from the first phase to a second crystalline phase having a higher k than the first phase. Likewise, RuO2 18 in physical contact with third dielectric metal oxide layer 50 during the annealing facilitates or imparts a change of the third dielectric metal oxide layer 50 from a third phase to a fourth crystalline phase having a higher k than the third phase. The first and third phases may be the same or may be different from one another. Regardless, processing may occur in any manner described above, and FIG. 14 depicts annealing having occurred of the FIG. 13 substrate.
In one embodiment, the annealed first, second and third dielectric layers are incorporated into a capacitor dielectric region 20d of a capacitor construction 22d comprising inner conductive capacitor electrode material 14b comprising RuO2 30 and an outer conductive capacitor electrode material 24 comprising conductive RuO2 18. Additional conductive layers may or may not be provided over RuO2 layer 18 as part of such outer conductive capacitor electrode.
In compliance with the statute, the subject matter disclosed herein has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the claims are not limited to the specific features shown and described, since the means herein disclosed comprise example embodiments. The claims are thus to be afforded full scope as literally worded, and to be appropriately interpreted in accordance with the doctrine of equivalents.

## Claims

1. A method of forming a capacitor, comprising:
depositing conductive capacitor electrode material over a substrate;
depositing a dielectric metal oxide layer over and into physical contact with the conductive capacitor electrode material;
depositing RuO2 over the dielectric metal oxide layer;
annealing the inner conductive capacitor electrode, the RuO2 and the dielectric metal oxide layer;
after the annealing and prior to any subsequent processing, etching utilizing an etch chemistry comprising O3 to selectively remove at least some of the RuO2; and
after the etching, forming conductive capacitor electrode material over the dielectric metal oxide layer.

2. A method of forming a capacitor, comprising:
depositing conductive capacitor electrode material over a substrate;
depositing a dielectric metal oxide layer over and into physical contact with the conductive capacitor electrode material;
depositing RuO2 over the dielectric metal oxide layer;
annealing the inner conductive capacitor electrode, the RuO2 and the dielectric metal oxide layer;
after the annealing, etching utilizing an etch chemistry comprising O3 to selectively remove at least some of the RuO2, the etch chemistry comprising a mixture consisting of O2 and O3, and wherein the mixture contains from 18% to 22% O3, by volume; and
after the etching, forming conductive capacitor electrode material over the dielectric metal oxide layer.