# Patent

## Title
Semiconductor devices including a ruthenium film

## Abstract

Methods for forming ruthenium films and semiconductor devices such as capacitors that include the films are provided.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application is a divisional of U.S. patent application Ser. No. 12/100,632, filed Apr. 10, 2008, now U.S. Pat. No. 8,124,528, issued Feb. 28, 2012.


TECHNICAL FIELD
Embodiments of the present disclosure relate to the field of semiconductor manufacture and, more particularly, to methods of forming a ruthenium metal layer in the fabrication of a semiconductor device, and devices resulting from those methods.
BACKGROUND OF THE INVENTION
Crystallographically textured tantalum oxide (Ta2O5) demonstrates approximately twice the dielectric permittivity of amorphous Ta2O5, making c-axis textured Ta2O5 very attractive as a DRAM cell dielectric. Metallic ruthenium is the bottom cell plate of choice for crystallographically textured, high permittivity Ta2O5 cell dielectrics because the Ta2O5 orders on the hexagonal close-packed (hcp) ruthenium structure and provides the high permittivity texturing.
Historically, there have been adhesion issues when ruthenium is deposited on silicon dioxide (SiO2) and other dielectric films. This adhesion issue on oxide dielectrics has been addressed by adding disilane (Si2H6) to the initial stages of ruthenium deposition. However, X-ray photoelectron spectrometry (XPS) analysis and secondary ion mass spectrography (SIMS) show that about 20 atomic percent silicon is present at the top surface of the deposited ruthenium film, which adversely affects the desired crystographically textured Ta2O5 deposition.
It would be desirable to provide a process for fabricating a ruthenium film that overcomes these problems.



BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention are described below with reference to the following accompanying drawings, which are for illustrative purposes only.
FIG. 1 is a diagrammatic cross-sectional view of a substrate at a preliminary step of a processing sequence.
FIGS. 2-6 are views of the substrate of FIG. 1 at subsequent processing steps according to according to an embodiment of the invention.
FIG. 7 is a block diagram of a circuit module according to an embodiment of the present invention.



DETAILED DESCRIPTION OF THE INVENTION
The following description provides illustrative examples of devices and methods according to embodiments of the present disclosure. Such description is for illustrative purposes only and not for purposes of limiting the same.
In the context of the current application, the terms “semiconductor substrate” or “semiconductive substrate” or “semiconductive wafer fragment” or “wafer fragment” or “wafer” will be understood to mean any construction comprising semiconductor material, including, but not limited to, bulk semiconductive materials such as a semiconductor 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, wafer fragments or wafers described above.
An embodiment of a method according to the invention is described with reference to FIGS. 1-6, in a method of forming an electrode in a capacitor construction.
Referring to FIG. 1, a substrate 10 (e.g., a wafer) is shown at a preliminary processing step in the formation of a capacitor. The substrate 10 in progress can comprise, for example, a semiconductor wafer substrate or the wafer along with various process layers formed thereon, including one or more semiconductor layers or other formations, and active or operable portions of semiconductor devices.
In the illustrated embodiment, the substrate 10 comprises a material layer 12 such as polysilicon, wordlines 14, and a diffusion region (active area) 16 formed in the material layer 12 between the wordlines, the diffusion region 16 being in the form of a source/drain region. A dielectric (insulative) material 18 such as borophosphosilicate glass (BPSG), phosphosilicate glass (PSG), or other oxide (e.g., SiOx, TEOS (tetraethyl orthosilicate), etc.) or other suitable insulative material has been formed on the material layer 12 and over the wordlines 14. A plug 20 comprising doped polycrystalline has been deposited into an opening through the dielectric material 18 as an electrical contact with the diffusion region 16. The foregoing structures can be formed by conventional methods known and used in the art. A container or opening 22 with sidewalls 23 and a base portion or floor 25, has been conventionally etched into the insulative layer 18 to expose the plug 20.
A lower electrode of ruthenium is then formed within the opening 22 within the insulative material layer 18.
Referring to FIG. 2, according to an embodiment of a method of the invention, an adhesion layer or nucleation (seed) layer 24 is formed on the insulative material layer 18 within the opening to improve adherence of the subsequently deposited ruthenium electrode layer to the insulative material layer 18. An adhesion layer 24 composed of ruthenium silicide (RuSix) can be formed, for example, by sputter depositing from a deposition target of RuSix, by physical vapor deposition (PVD) of RuSix, by atomic layer deposition (ALD), or by chemical vapor deposition (e.g., CVD, LPCVD, APCVD, PECVD, etc.) using a silicon precursor gas and a ruthenium precursor gas.
In other embodiments, the adhesion (seed) layer 24 can be composed of RuSixOy and formed, for example, by a process as described, for example, in U.S. Pat. No. 6,461,909 to Marsh et al.
In the illustrated embodiment, an RuSix adhesion layer 24 is formed by CVD, for example, by exposing the substrate 10 to a gaseous mixture of a silicon precursor gas and a ruthenium precursor gas at a ratio of about 50:1 to about 1:1 for a duration of about 0.5-20 seconds, or about 1-10 seconds to form the adhesion layer 24 to a thickness of about 1-20 angstroms, or about 1-10 angstroms. In embodiments of the method, the flow rate of the silicon precursor is about 1-100 sccm (or about 20-80 sccm), the flow rate of the ruthenium precursor is about 1-20 sccm (or about 1-10 sccm), and the flow rate of an optional carrier gas is about 50-1000 sccm (or about 200-500 sccm). General CVD processing parameters include a deposition pressure of about 0.1-20 torr, and a deposition temperature at the substrate surface of about 100° C. to 700° C. or about 200° C. to 500° C.
In some embodiments, the silicon precursor is initially deposited onto the insulative material layer 18 to form a thin seed layer ranging from a monolayer (e.g., about 2 angstroms to about 5 angstroms thick). Both the silicon and ruthenium precursors can then be flowed into the reaction chamber to deposit the RuSix adhesion layer 24.
Examples of silicon precursor gases include a silicon hydride or silane such as silane (SiH4), disilane (Si2H6), trisilane (Si3H8), dichlorosilane (DCS, SiH2Cl2), trichlorosilane (TCS, SiHCl3), hexachlorodisilane (Si2Cl6), trisilylamine (N(SiH3)3), methylated silanes, among others.
Any ruthenium containing precursor can be used in accordance with the present disclosure. Typical ruthenium precursors for CVD deposition include liquid ruthenium metal-organic precursors. The ruthenium precursor can be contained in a bubbler reservoir through which a carrier gas, such as helium or any other inert gas (e.g., nitrogen, argon, neon, and xenon), is bubbled through the reservoir containing the precursor to deliver the precursor to a reaction chamber. For example, a carrier gas having a volumetric flow rate in the range of about 1-500 sccm can be used in a bubbler reservoir having a pressure in the range of about 0.5-50 torr and a temperature in the range of about 30° C. to 70° C. to deliver a ruthenium precursor to the reaction chamber.
Ruthenium precursors include liquid ruthenium complexes of the following formula: (diene)Ru(CO)3, wherein “diene” refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, fluorinated derivatives thereof, combinations thereof, and derivatives thereof additionally containing heteroatoms such as halide, Si, S, Se, P, As, or N, as described, for example, in U.S. Pat. Nos. 6,063,705 and 5,962,716.
For example, the ruthenium precursor can be a ruthenocene having the formula (Cp′)Ru or (Cp′)Ru(Cp′′), where Cp′ and Cp′′ can be the same or different and have the following formula:




wherein R1-R5 can be independently selected from the group consisting of H, F, and straight-chained or branched C1-C5 alkyl groups (e.g., Me, Et, i-propyl, n-propyl, t-butyl, n-butyl, sec-butyl, n-amyl, i-amyl, t-amyl, etc.). Nonlimiting examples of suitable ruthenocenes include bis(cyclopentadienyl)ruthenium, bis(ethylcyclopentadienyl)ruthenium, and bis(pentamethylcyclopentadienyl)ruthenium.

The ruthenium precursor can also be a ruthenium β-diketonate having the formula Ru(β-diketonate)3, wherein the β-diketonate has the formula:




wherein R1 and R2 can be independently selected from the group consisting of H, F, straight-chained or branched C1-C5 alkyl groups (e.g., Me, Et, i-propyl, n-propyl, t-butyl, n-butyl, sec-butyl, n-amyl, t-amyl, etc.), and fluorine-substituted straight-chained or branched C1-C5 alkyl groups (e.g., Me, Et, i-propyl, n-propyl, t-butyl, n-butyl, sec-butyl, n-amyl, i-amyl, t-amyl, etc.). Nonlimiting examples of β-diketonates include 2,4-pentanedionate; 1,1,1-trifluoro-2,4-pentanedionate; 2,2,6,6-tetramethyl-3,5-heptanedionate; 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; 2,2,7-tetramethyl-3,5-octanedionato; 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato; and 2,4-octanedionato. In an embodiment, R1 and R2 are independently selected from the group consisting of C1-C5 fluoroalkyl groups.

The ruthenium precursor can also be a ruthenium carbonyl such as Ru(CO)5, Ru3(CO)12, Ru(CO)9, (C6H8)Ru(CO)3, and (C7H10)Ru(CO)3, and cyclopentadienyl dicarbonyl ruthenium (II) dimer.
Additional precursors and methods of depositing ruthenium layers are generally discussed in U.S. Pat. No. 5,372,849 to McCormick et al. (Minnesota Mining and Manufacturing Company (St. Paul, Minn.)).
A carrier gas can be used to deliver the precursor gas(es) to the reaction chamber, for example, an inert gas such as helium, nitrogen, neon, xenon, and/or argon. Optionally, a carrier or dilution gas (e.g., He, Ar, etc.) can be introduced into the reaction chamber to alter the concentrations of the gases therein, for example, at a varied flow rate. Oxidizing gases can also be introduced into the reaction chamber when desired.
Referring now to FIG. 3, a ruthenium layer or film 26 is then formed on the adhesion or nucleation (seed) layer 24 by chemical vapor deposition processing (e.g., CVD, LPCVD, APCVD, PECVD, etc.). The flow of the silicon precursor is terminated and a hydrogen source gas is flowed with the ruthenium precursor gas to form a hydrogen-treated ruthenium layer 26. In embodiments of the method, the hydrogen source gas is hydrogen gas (H2), and in other embodiments, ammonia (NH3) is used. Optionally, a carrier gas (e.g., He, Ar, etc.) can be used. CVD processing conditions can be as described for forming the RuSix adhesion layer 24. The ruthenium layer 26 can by formed by CVD, for example, by exposing the substrate 10 to a gaseous mixture of a ruthenium precursor gas and a hydrogen source gas (e.g., H2 or NH3) at a ratio of about 0.001:1 to about 1:1 for a duration effective to deposit the desired thickness, generally at least about 100 angstroms, e.g., about 100-300 angstroms, or about 150-250 angstroms. In embodiments of the method, the flow rate of the ruthenium precursor is about 1-20 sccm (or about 1-10 sccm), and the flow rate of the hydrogen source gas is at least about 200 sccm, and in other embodiments at least about 400 sccm (e.g., about 400-600 sccm). The flow rate of an optional carrier gas can be about 50-1000 sccm (or about 200-600 sccm). In an embodiment, the ruthenium precursor gas flows continuously during CVD processing as the flow of the silicon precursor gas is terminated and flow of the hydrogen source gas is commenced.
The incorporation of hydrogen in the ruthenium layer 26 functions to reduce or eliminate the diffusion of silicon into the bulk ruthenium layer to below detectable levels, particularly in the upper surface of the ruthenium layer 26 (e.g., to a depth of about 10-30 angstroms). The incorporation of hydrogen can further function to promote densification and reduce the porosity of the ruthenium layer 26, increase the stability of the ruthenium layer in air, and improve the uniformity of the ruthenium layer.
Optionally, as depicted in FIG. 4, in some embodiments, the flow of the hydrogen source gas can be terminated and the ruthenium precursor gas can be flowed to form an additional ruthenium layer 28 over the hydrogen-treated ruthenium layer 26. The ruthenium layer 28 can be formed to a desired thickness at about 0 angstroms to 300 angstroms, or about 0 angstroms to 100 angstroms. The combined layers 24, 26, 28 form a lower electrode 30, which typically has a total thickness of about 50 angstroms to 300 angstroms, or about 50 angstroms to 100 angstroms.
Due, at least in part, to the addition of the hydrogen source gas during the formation of the ruthenium material layer 26, diffusion of silicon from the initial adhesion (seed) layer 24 into the upper portion of the hydrogen-treated ruthenium layer 26 is eliminated and the surface 32 of the ruthenium electrode 30 is substantially or completely silicon-free, i.e., 0 atomic percent to 0.01 atomic percent silicon by X-ray photoelectron spectroscopy (XPS) and/or secondary ion mass spectroscopy (SIMS) analysis. The resulting ruthenium electrode 30 is a graded layer with the content (atomic percent) of ruthenium increasing and the silicon concentration decreasing from the adhesion layer (e.g., RuSix) 24 to the surface 32 of the ruthenium electrode 30 (e.g., the surface of the hydrogen-treated ruthenium layer 26). In some embodiments, the ruthenium electrode 30 is a graded layer in which the adhesion layer 24 (e.g., RuSix) has a high silicon content of about 10 atomic percent to 90 atomic percent and ruthenium content of about 10 atomic percent to 90 atomic percent, with the silicon content decreasing progressively through the hydrogen-treated ruthenium layer 26 to a non-detectable level (i.e., 0 atomic percent to 0.01 atomic percent) at the surface 32 of the ruthenium electrode 30. In some embodiments, the ruthenium electrode 30 has a surface atomic concentration of ruthenium greater than about 50 atomic percent, or about 50 atomic percent to 80 atomic percent with the resistivity of the film at about 100-1,000% of the bulk ruthenium.
The resulting electrode 30 has a lowered resistivity (Rs value), improved film uniformity, and higher film stability, e.g., in an ambient environment, with little or no degradation occurring upon exposure to air.
Referring now to FIG. 5, a dielectric (insulating) layer 34 is formed on the surface 32 of the ruthenium electrode 30. In embodiments of the invention, the dielectric layer 34 comprises a dielectric material having a high dielectric constant, for example, greater than about 7, or greater than about 50. In some embodiments, the dielectric layer 34 comprises tantalum oxide Ta2O5, and/or other metal oxide dielectric material, for example, barium strontium titanate (BaxSr(1-x)TiO3 (BST) where 0<x,1), BaTiO3, SrTiO3, PbTiO3, Pb(Zr,Ti)O3 (PZT), (Pb,La)(Zr,Ti)O3 (PLZT), (Pb,La)TiO3, (PLT), Ta2O5, KNO3, LiNbO3, HfO2, and/or Al2O3, among others. The dielectric layer 34 can be formed by conventional methods, for example, RF-magnetron sputtering, chemical vapor deposition (CVD), or other suitable deposition method. The dielectric layer 34 (e.g., Ta2O5) formed on the ruthenium electrode 30 is properly crystallized with a textured, hexagonal crystalline structure or phase, or will crystallize upon a moderate (about 400° C. to 650° C.) thermal anneal.
The dielectric layer can also be formed from a low-k dielectric material, for example, SiO2, Si3N4, or a composite thereof.
As illustrated in FIG. 6, a conductive material is then deposited to form a top electrode or plate 36 of a capacitor 38. The top electrode 36 can be formed of any conductive material, for example, a metal (e.g., ruthenium, platinum, rhodium, etc.), a conductive metal oxide (e.g., ruthenium oxide, iridium oxide, etc.), or doped polysilicon. The layers can then be patterned by known techniques as conventional in the art, and the substrate 10 further processed as desired.
FIG. 7 is a block diagram of an embodiment of a circuit module 40 in which the present invention can be incorporated. Such modules, devices and systems (e.g., processor systems) incorporating such a module are described and illustrated in U.S. Pat. No. 6,437,417 (Gilton) and U.S. Pat. No. 6,465,828 (Agarwal), the disclosures of which are incorporated by reference herein. In brief, two or more dice 42 may be combined into a circuit module 40 to enhance or extend the functionality of an individual die 42. Circuit module 40 can be a combination of dice 42 representing a variety of functions, or a combination of dice 42 containing the same functionality. One or more dice 42 of the circuit module 40 can contain circuitry, or integrated circuit devices that include at least one ruthenium layer 30 or capacitor 30 or other device incorporate the ruthenium layer 30 in accordance with the embodiments of the present invention. The integrated circuit devices can include a memory cell that comprises a ruthenium layer as discussed in the various embodiments in accordance with the invention.
Some examples of a circuit module include memory modules, device drivers, power modules, communication modems, processor modules, and application-specific modules, and may include multi-layer, multi-chip modules. Circuit module 40 can be a subcomponent of a variety of electronic systems, such as a clock, a television, a cell phone, a personal computer, an automobile, an industrial control system, an aircraft, among others. Circuit module 40 will have a variety of leads 44 extending therefrom and coupled to the dice 42 providing unilateral or bi-lateral communication and control.
The circuit module 40 can be incorporated, for example, into an electronic system that comprises a user interface, for example, a keyboard, monitor, display, printer, speakers, etc. One or more circuit modules can comprise a microprocessor that provides information to the user interface, or is otherwise programmed to carry out particular functions as is known in the art. The electronic system can comprise, for example, a computer system including a processor and a memory system as a subcomponent, and optionally user interface components, and other associated components such as modems, device driver cards, etc. Examples of memory circuits include, but are not limited to, DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), flash memories, a synchronous DRAM, such as SGRAM (Synchronous Graphics Random Access Memory), SDRAM (Synchronous Dynamic Random Access Memory), SDRAM II, and DDR SDRAM (Double Data Rate SDRAM), as well as Synchlink or Rambus DRAMs and other emerging memory technologies.
Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement which is calculated to achieve the same purpose can be substituted for the specific embodiments shown. This application is intended to cover any adaptations or variations that operate according to the principles of this disclosure as described herein. It is therefore intended that such changes and modifications be covered by the appended claims and the equivalents thereof. The disclosures of patents, references and publications cited in the application are incorporated by reference herein.

## Claims

1. A semiconductor device, comprising;
an adhesion material comprising silicon and ruthenium on a substrate; and
a ruthenium material overlying and in contact with the adhesion material, the ruthenium material having a surface with a silicon content of between 0 atomic percent and 0.01 atomic percent.

2. The semiconductor device of claim 1, wherein the ruthenium material comprises an increasing concentration of ruthenium and a decreasing concentration of silicon extending from the adhesion material to the surface of the ruthenium material, an upper portion of the ruthenium material substantially free of silicon.

3. The semiconductor device of claim 1, further comprising another ruthenium material over the ruthenium material, the ruthenium material comprising a reduced porosity than the another ruthenium material.

4. The semiconductor device of claim 1, wherein the adhesion material comprises ruthenium, silicon, and oxygen.

5. The semiconductor device of claim 1, wherein the ruthenium material comprises ruthenium and hydrogen.

6. A semiconductor device, comprising:
an adhesion material comprising ruthenium and silicon on a substrate;
a ruthenium material overlying and in contact with the adhesion material, the ruthenium material having an increasing concentration of ruthenium and a decreasing concentration of silicon extending from the adhesion material to a surface of the ruthenium material, and the surface of the ruthenium material substantially free of silicon; and
another ruthenium material over the ruthenium material, the ruthenium material comprising a reduced porosity than the another ruthenium material.

7. The semiconductor device of claim 6, wherein the surface of the ruthenium material is substantially free of silicon to a depth of from about 10 angstroms to 30 angstroms.

8. The semiconductor device of claim 6, wherein the silicon concentration of the adhesion material is between about 10 atomic percent and 90 atomic percent and the silicon concentration at the surface of the ruthenium material is between O atomic percent and 0.01 atomic percent.

9. The semiconductor device of claim 6, wherein the ruthenium material is between about 50 angstroms and 300 angstroms thick.

10. The semiconductor device of claim 6, wherein the adhesion material is between about 2 angstroms and 50 angstroms thick.

11. The semiconductor device of claim 6, wherein the adhesion material is about a monolayer thick.

12. The semiconductor device of claim 6, wherein the adhesion material consists essentially of ruthenium silicide.

13. The semiconductor device of claim 6, wherein the ruthenium material contains no oxygen.

14. A semiconductor device, comprising:
an adhesion material comprising ruthenium silicide on a substrate; and
a ruthenium material overlying and in contact with the adhesion material, wherein the ruthenium material comprises an increasing concentration of ruthenium and a decreasing concentration of silicon extending from the adhesion material to a surface of the ruthenium material and the silicon content at the surface of the ruthenium material is between about 0 atomic percent and 0.01 atomic percent.

15. The semiconductor device of claim 14, wherein the substrate comprises silicon.

16. The semiconductor device of claim 14, wherein the substrate comprises borophosphosilicate glass, phosphosilicate glass or silicon nitride.

17. A semiconductor device, comprising:
an adhesion material comprising ruthenium and silicon on a substrate;
a ruthenium material overlying and in contact with the adhesion material, the ruthenium material comprising an increasing concentration of ruthenium and a decreasing concentration of silicon extending from the adhesion material to a surface of the ruthenium material, wherein the silicon concentration at the surface of the ruthenium material is between 0 atomic percent and 0.01 atomic percent; and
a dielectric material overlying the ruthenium material.

18. The semiconductor device of claim 17, wherein the dielectric material comprises a high-K dielectric material.

19. The semiconductor device of claim 18, wherein the high-K dielectric material comprises tantalum oxide.

20. A capacitor, comprising a lower electrode, the lower electrode comprising:
an adhesion material comprising ruthenium and silicon overlying and in contact with a dielectric material; and
a ruthenium material overlying and in contact with the adhesion material, wherein the ruthenium material comprises an increasing concentration of ruthenium and a decreasing concentration of silicon extending from the adhesion material to a surface of the ruthenium material, wherein the silicon content at the surface of the ruthenium material is between about 0 atomic percent and 0.01 atomic percent.

21. The capacitor of claim 20, wherein the lower electrode is situated within an opening in the dielectric material.

22. The capacitor of claim 20, further comprising a high-K dielectric material over and in contact with the ruthenium material.

23. The capacitor of claim 22, wherein the high-K dielectric material comprises tantalum oxide having a hexagonal crystalline structure throughout.

24. The capacitor of claim 22, further comprising a conductive material over the high-K dielectric material.

25. An integrated circuit supported by a substrate, and comprising a ruthenium material overlying and in contact with an adhesion material comprising silicon and ruthenium, wherein the ruthenium material comprises an increasing concentration of ruthenium and a decreasing concentration of silicon extending from the adhesion material to a surface of the ruthenium material, the silicon content at the surface of the ruthenium material between about 0 atomic percent and 0.01 atomic percent.