SOLID SOURCE METAL-ORGANIC MOLECULAR BEAM EPITAXY FOR DEPOSITION OF ULTRA-LOW VAPOR PRESSURE METALS AND METAL OXIDES

Abstract

A system includes a vacuum chamber, and a substrate in the vacuum chamber includes a target surface. At least one effusion cell is in the vacuum chamber, wherein the effusion cell contains a solid metal-organic precursor compound with a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C. The effusion cell is configured to sublime the solid metal-organic precursor compound at a sublimation temperature greater than about 0 C. and less than about 200 C. such that a stream of metal particles from the solid metal-organic precursor compound emanate from the effusion cell are directed toward to the target surface of the substrate to form a coating thereon.

Claims

1. A system, comprising: a vacuum chamber; a substrate in the vacuum chamber, wherein the substrate comprises a target surface; and at least one effusion cell in the vacuum chamber, wherein the effusion cell contains a solid metal-organic precursor compound with a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C., and wherein the effusion cell is configured to sublime the solid metal-organic precursor compound at a sublimation temperature greater than about 0 C. and less than about 200 C. such that a stream of metal particles from the solid metal-organic precursor compound that emanate from the effusion cell are directed toward to the target surface of the substrate to form a coating thereon.

2. The system of claim 1, wherein the sublimation temperature is less than about 85 C.

3. The system of claim 1, wherein the solid metal-organic precursor compound comprises a metal chosen from Pt, Ru, Ir, W, and mixtures and combinations thereof.

4. The system of claim 3, wherein the solid metal-organic precursor compound comprises a -diketonate with a metal chosen from Pt, Ir, Ru, and combinations thereof.

5. The system of claim 1, wherein the target surface is heated to a temperature of about 400 C. to about 930 C.

6. The system of claim 1, wherein the target surface comprises SrTiO.sub.3.

7. The system of claim 1, further comprising an oxygen source configured to direct a beam of oxygen atoms toward the target surface.

8. The system of claim 1, wherein the vacuum chamber is free of a carrier gas.

9. The system of claim 1, wherein the coating comprises a thin film, and wherein the thin film comprises Pt.

10. A method for making a coating, the method comprising: subliming at a sublimation temperature of greater than about 0 C. and up to about 200 C. a solid metal-organic precursor compound having a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C. to form a flow of metal particles; and directing the flow of metal particles toward a target surface to form the coating thereon.

11. The method of claim 10, wherein the sublimation temperature is about 65 C. to about 85 C.

12. The method of claim 10, wherein the solid metal-organic precursor compound comprises a -diketonate with a metal chosen from Pt, Ir, Ru, and combinations thereof.

13. The method of claim 10, wherein the target surface comprises SrTiO.sub.3.

14. The method of claim 10, further comprising directing a flow of oxygen atoms toward the target surface.

15. A metal coating on a substrate, wherein the metal coating is formed from a stream of metal particles derived from subliming at a sublimation temperature of greater than about 0 C. and up to about 200 C. a solid metal-organic precursor compound having a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C.

16. The metal coating of claim 15, wherein the sublimation temperature is about 65 C. to about 85 C.

17. The metal coating of claim 15, wherein the solid metal-organic precursor compound comprises a metal chosen from Pt, Ru, Ir, W, and mixtures and combinations thereof.

18. The metal coating of claim 17, wherein the solid metal-organic precursor compound comprises a -diketonate with a metal chosen from Pt, Ir, Ru, and combinations thereof.

19. The metal coating of claim 15, wherein the metal coating is a single crystalline Pt film.

20. The metal coating of claim 19, wherein the Pt film has a thickness of about 50 nm to about 100 nm.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0014] FIG. 1 is a schematic cross-sectional view of an example embodiment of a solid-source molecular beam epitaxy (MBE) system according to the present disclosure.

[0015] FIG. 2 is a plot of the temperature dependent vapor pressure of various metals that can potentially be used in MBE deposition processes. The melting points are shown as open circles and dashed lines are linear extrapolations. The typical vapor pressure range used in MBE is highlighted.

[0016] FIG. 3(a) is a plot of the temperature dependent vapor pressure of the platinum containing metal-organic precursor used in the examples, Pt(acac).sub.2, compared to commonly used metals and metal-organics. The open circle is the melting point and dashed lines are linear extrapolations.

[0017] FIG. 3(b) is a schematic depiction of the deposition technique used in the examples.

[0018] FIGS. 4(a)-(g) are structural characterizations of platinum on SrTiO.sub.3 substrates obtained as described in the examples below.

[0019] FIG. 4(a) is a high-resolution x-ray diffraction (HRXRD) image of Pt films on SrTIO.sub.3 (001) substrates of Example 1 with increasing substrate temperature from bottom to top.

[0020] FIGS. 4(b), (d) and (f) are reflection high-energy electron diffraction (RHEED) patterns, and FIGS. 4(c) (e) and (g) are atomic force microscope (AFM) images, of substrate temperatures 930 C., 760 C., and 630 C., respectively for the coatings of Example 1.

[0021] FIGS. 5(a)-(d) show structural characterization of platinum on Nb-doped SrTiO.sub.3 substrates and resistivity on undoped SrTiO.sub.3 as described in Examples 2-3.

[0022] FIG. 5(a) is a HRXRD plot, FIG. 5(b) is a RHEED pattern, and FIG. 5(c) is an AFM image of a 70 nm platinum film on conducting Nb-doped SrTO.sub.3 (001) substrate.

[0023] FIG. 5(d) is a plot of temperature dependent resistivity of a 70 nm platinum film on an insulating SrTiO.sub.3 (001) substrate. The red line is a fit to the Bloch-Grneisen equation.

[0024] FIG. 6 is a schematic diagram of residual resistivity ratios of Pt films of the present disclosure compared to values obtained from literature reports from e-beam evaporation and magnetron sputtering PVD techniques. The techniques are ordered based on the rough cost/complexity of supplying the Pt metal.

[0025] FIG. 7(a) is HRXRD plot of RuO.sub.2 films on r-plane Al.sub.2O.sub.3 substrates with varying substrate temperature as described in Example 4.

[0026] FIGS. 7(b)-(c) show RHEED patterns of a film grown at 300 C.

[0027] FIG. 7(d) is an AFM image of a film grown at 300 C.

[0028] FIG. 7(e) is a plot of the full-width half maximum (FWHM) vs. substrate temperature of a RuO.sub.2 (101) rocking curve.

[0029] FIG. 7(f) is a plot of resistivity vs temperature of films grown at 300 C. with different thicknesses compared to the bulk (black).

[0030] FIG. 8(a) is a HRXRD plot of 6-10 nm RuO.sub.2 films on various substrates as described in Example 5. Bulk RuO.sub.2 and SnO.sub.2 expected peak positions are indicated by the black and gray dashed lines, respectively. Substrate peaks are indicated by asterisks.

[0031] FIG. 8(b) is a plot of resistivity vs temperature of the films of FIG. 8(a) compared to the bulk materials.

[0032] Like symbols in the drawings indicate like elements.

DETAILED DESCRIPTION

[0033] Referring now to FIG. 1, a system 10 for depositing a coating using solid source molecular beam epitaxy (MBE) includes a vacuum chamber 12 evacuated by a vacuum pump system 14. An effusion cell 16 is located within the vacuum chamber 12. A solid metal-organic precursor compound 18, which includes a metal to be deposited on a target surface 50 of a substrate 52, is within the effusion cell 16.

[0034] In various embodiments, the substrate 52 may be any material capable of supporting a deposited metal coating. For example, in some embodiments the target surface 50 of the substrate 52 may be made of Si, SiO.sub.2, Al.sub.2O.sub.3, AlN, SrTiO.sub.3, or other crystalline materials depending on the desired application. In some embodiments, the target surface may optionally be doped with another element to, for example, provide a preferred structure for the as-deposited metal film or coating. In one non-limiting example, the SrTiO.sub.3 substrate may be doped with Nb, La, Nd and mixtures and combinations thereof.

[0035] The solid metal-organic precursor compound has a vapor pressure of less than about 10.sup.2 Torr, or about 10.sup.2 Torr to about 10.sup.5 Torr, at a temperature over a temperature range of about 25 C. to about 300 C. When activated, the effusion cell 16 heats the solid metal-organic precursor compound 18 to a temperature of less than about 300 C., or less than about 100 C., or less than about 85 C., or less than about 65 C., and causes the metal-organic precursor compound to sublime, which produces a flow or beam 20 of metal particles 22 directed toward the target surface 50. The metal particles 22 collect on the target surface 50 to produce a thin film coating 54 of the metal liberated from the metal-organic precursor compound 18, while the accompanying organics are not incorporated.

[0036] In some embodiments, the system 10 includes an optional oxygen source 30 configured to supply a flow of oxygen atoms 32 (for example, O, O.sub.2, O.sub.3 and the like) toward the target surface 50. In various embodiments the oxygen atoms 32 can be used to, for example, oxidize the coating 54 or control the orientation of the metal in the coating 54. In one example embodiment, the oxygen source 30 may be used to control the (001) orientation of Pt atoms deposited in the coating 54.

[0037] The system 10 includes an optional heater 40 to heat the substrate 52 and the target surface 50. In some embodiments, the heater 40 can heat the target surface 50 to a temperature of about 400 C. to about 1000 C., or about 450 C. to about 950 C., or about 500 C. to about 850 C. In some examples, selecting the temperature of the target surface 50 can impact one or more structural characteristics of the coating 54.

[0038] In some embodiments, the system 10 includes one or more optional additional effusion cells 36 including a metal or metal-organic precursor compound 38, which may be the same or different from the metal-organic precursor compound 18 in the effusion cell 16. The effusion cell 36 sublimes the metal-organic precursor compound 38 to produce a flow or beam 37 of metal particles 39 directed toward the target surface 50. In various embodiments, the additional effusion cells 36 may be used to form more complex binary or ternary coatings 54 including the metal particles 39, or may be used to increase an overall deposition rate of the metal particles onto the target surface 50.

[0039] The system 10 does not require a carrier gas be supplied to the vacuum chamber 12, and the lack of a carrier gas increases the mean free path of the metal particles 22, 39 and the oxygen atoms 32, allowing for increased material structural quality. However, in some embodiments the system 10 can include an optional carrier gas source 42 to supply a carrier gas to the vacuum chamber 12.

[0040] In various examples shown schematically in FIG. 1, the various components in the system 10 may be interfaced with a controller 70 having at least one processor 72. The controller 70 may be configured to control one or more parameters of the effusion cells 16, 36, the oxygen source 30, the heater 40, the vacuum pump 14, or the carrier gas source 42 to determine one or more physical or chemical properties of the coating 54.

[0041] In some examples, the controller 70 may be configured to process detected signals from one or more sensor systems 74 in the vacuum chamber 12 or on the system 10. The processor 72 may be integrated with the sensor systems 74, may be integrated with the controller 70, or may be a remote processor functionally connected to the controller 70.

[0042] The processor 72 may be any suitable software, firmware, hardware, or combination thereof. The processor 72 may include any one or more microprocessors, controllers, digital signal processors (DSPs), application specific integrated circuits (ASICs), field-programmable gate arrays (FPGAs), or discrete logic circuitry. The functions attributed to the processor 72 may be provided by processing circuitry of a hardware device, e.g., as supported by software and/or firmware.

[0043] In some examples, the processor 72 may be coupled to a memory device 76, which may be part of the controller 70 or remote thereto. The memory device 76 may include any volatile or non-volatile media, such as a random-access memory (RAM), read only memory (ROM), non-volatile RAM (NVRAM), electrically erasable programmable ROM (EEPROM), flash memory, and the like. The memory device 76 may be a storage device or other non-transitory medium. The memory device 76 may be used by the processor 72 to, for example, store fiducial information or initialization information corresponding to, for example, sublimation temperatures for the metal-organic precursor compounds 18, 38, angles of the effusion cells 16, 36 or the oxygen source 30 with respect to the target surface 50, target deposition rates for the metal-organic precursor compounds 18, 38, surface geometries of formed coatings 54, temperatures of the target surface 50, pressure within the vacuum chamber 14, or deposition and process times. In some examples, the memory device 76 may store determined values of any of these parameters for later retrieval.

[0044] In some embodiments, the controller 70 and the processor 72 are coupled to a user interface 78, which may include a display, user input, and output (not shown in FIG. 1). Suitable display devices include, for example, monitor, PDA, mobile phone, tablet computers, and the like. In some examples, user input may include components for interaction with a user, such as a keypad and a display such as a cathode ray tube (CRT) display, a liquid crystal display (LCD) or light emitting diode (LED) display, and the keypad may take the form of an alphanumeric keypad, or a reduced set of keys associated with particular functions. In some examples, the displays may include a touch screen display, and a user may interact with user input via the touch screens of the displays. In some examples, the user may also interact with the user input remotely via a networked computing device.

[0045] The controller 70 can be configured to control any selected number of functions of the system 10 in response to signals from the processor 72 input manually into the controller 70, or stored in the memory device 76. In some examples, the controller 70 can be configured to generate control signals obtained from, for example, one or more sensors in the sensor system 74, to provide closed loop control of the parameters of the effusion cells 16, 36, the oxygen source 30, and the like to control the deposition of the coating 54.

[0046] In various examples, the controller 70 may be adjusted by a variety of manual and automatic means. Automatic means may make use of any number of control algorithms or other strategies to achieve desired conformance to a predetermined set of properties of the coating 54. For example, standard control schemes as well as adaptive algorithms such as so-called machine-learning algorithms may be used. In some examples, controller 70 can utilize information from other sources such as, for example, infrared cameras, to determine the control action decided by algorithms such as PID control schemes or machine learning schemes.

[0047] The metal-organic precursor compounds 18, 38 may include any organometallic or metal-organic compound in which a metal to be deposited is associated with an organic group. In various embodiments, the metal may be complexed with or bound to the organic group in a wide variety of ways including ionic or covalent bonding.

[0048] In various embodiments, the metal-organic precursor compound should have a vapor pressure of less than about 10.sup.2 Torr to about 10.sup.5 Torr over a working range of about 25 C. to about 300 C. and as such readily sublimes in the low-temperature effusion cells 16, 36. In various embodiments, the metal-organic precursor compounds should sublime to release a bound metal atom at a sublimation temperature of greater than about 25 C. to less than about 300 C. or less than about 200 C., or less than about 150 C., or less than about 100 C., or less than about 85 C. or even less than about 65 C. The metal-organic precursor compound should also be substantially thermally stable up to the sublimation temperature.

[0049] In various embodiments, which are not intended to be limiting, the metal-organic precursor compound can be complexed with or bound to any metal. The systems and processes of the present disclosure metals have been found especially suitable to deposit metals with low vapor pressures. As shown in FIG. 2, suitable examples include, but are not limited to Pt, Ru, Ir, Os, W, and alloys and mixtures thereof.

[0050] In various embodiments, any of these low vapor pressure metals may be bound to or complexed with an organic group such as a diketonate. In some examples, which are not intended to be limiting, the diketonate may be acetylacetonate (acac), phenylacetonates (phac), and the like. In one example, the solid metal-organic precursor compound includes a -diketonate with a metal chosen from Pt, Ir, Ru, and combinations thereof such as for example, platinum (II) acetylacetonate (Pt(acac).sub.2), ruthenium (III) acetylacetonate (Ru(acac).sub.3) and iridium (III) acetylacetonate (Ir(acac).sub.3).

[0051] As examples, the temperature dependent vapor pressure of Pt(acac).sub.2 and (Ru(acac).sub.3 are shown in the plots of FIG. 3(a). FIG. 3(a) shows the vapor pressure of Pt(acac).sub.2 and Ru(acac).sub.3 compared to metallic elements like Ba and Sr, and volatile metal-organics like vanadium (V) oxytriisopropoxide (VTIP), titanium(IV) tetraisopropoxide (TTIP), and hexamethylditin (HMDT). Pt(acac).sub.2 and Ru(acac).sub.3 are also solids at these temperatures, with a melting point of 240 C. and 260 C., respectively, which is important for its ease of use in an effusion cell. Finally, Pt(acac).sub.2 and Ru(acac).sub.3 are thermally stable until about 210 C. and 230 C., respectively, indicating thermal decomposition should not occur. Utilizing these materials can take advantage of the inherent oxidation state of the metal in the metal-organic complex, which can be useful as stabilizing some metals in a desired oxidation state can be difficult.

[0052] In various embodiments, the coating 54 formed on the target surface 50 of the substrate 52 may include one or more of the low vapor pressure metals with a vapor pressure of about 10.sup.2 Torr to about 10.sup.5 Torr discussed above such as, Pt, Ir, Ru, W, mixtures and combinations thereof, and oxides thereof. In some embodiments, the coating 54 consists essentially of Pt, Ir, Ru or W, and in some embodiments, the coating 54 consists of Pt, Ir, Ru or W. In various embodiments, the coating 54 may be a single crystalline thin film of any of Pt, Ir, Ru or W or an alloy or an oxide thereof.

[0053] In various embodiments, which are not intended to be limiting and provided as examples, the coating 54 may have a thickness of about 50 nm to about 100 nm, or larger simply depending on coating time.

[0054] In some embodiments, the coating 54 may include Pt films with a resistivity () at room temperature of about 15 cm, or similar to bulk Pt 10.6 cm. The coating 54 may in some cases have a residual resistivity ratio (RRR) of greater than about 25.

[0055] In another embodiment, the present disclosure is directed to a method for making a metal coating, which includes subliming at a sublimation temperature of greater than about 0 C. and up to about 300 C. a solid metal-organic precursor compound having a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C. to form a flow of metal particles; and directing the flow of metal particles toward a target surface to form the coating thereon.

[0056] As noted above, in some examples the substrate 52 including the coating 54 may be utilized as an electronic component or may form a portion of an electronic component such as, for example, a capacitor plate, transistor, diode, or other portions of integrated circuits.

[0057] The systems and methods of the present disclosure will now be further described in the following non-limiting examples.

EXAMPLES

[0058] An effusion cell (E-Science, Inc., Hudson, WI, US) was used for the low temperature, 65-85 C., sublimation of Pt(acac).sub.2 (97%, MilliporeSigma, Burlington, MA, US). The powder metal-organic precursor compound was placed directly in a pyrolytic boron nitride (PBN) crucible (E-Science. Inc., US) inside an effusion cell. At 65 C. a beam equivalent pressure (BEP) of 210.sup.7 was measured.

Example 1

[0059] Platinum films were grown in an oxygen environment to stabilize the (001) epitaxial orientation. Oxygen was supplied at a pressure of 510.sup.6 torr by an rf plasma source (Mantis Deposition Ltd., Thame, UK) operated at 250 W and with charge deflection plates. Epitaxial platinum films were grown on SrTiO.sub.3 (001) and Nb-doped SrTiO.sub.3 (001) single crystal substrates (Crystec GmbH, Berlin, DE). The substrate surfaces were cleaned for 30 minutes in oxygen plasma prior to growth. Substrate temperatures were varied from 400-930 C., calibrated from the effusion cell power supply voltage and current. Following growth, the films were kept in an oxygen plasma environment during cooling to ensure the (001) orientation and phase purity.

[0060] Reflection high-energy electron diffraction (RHEED, Staib Instruments, Langenbach, DE) was carried out in-situ during and after growth to monitor the platinum film surface. Film surfaces after growth were also characterized using atomic force microscopy (AFM). High-resolution x-ray diffraction (HRXRD) was performed using a system available under the trade designation SmartLab SE from Rigaku Analytical Devices, Wilmington, MA, for structural characterization. Temperature dependent four terminal resistivity measurements were performed using indium as an ohmic contact in a Physical Properties Measurement System available under the trade designation PPMS DynaCool from Quantum Design. San Diego, CA, down to 1.8 K.

[0061] Single platinum (002) peaks were present in the HRXRD plot, as seen in FIG. 4(a), down to 520 C. showing a phase pure film with an epitaxial (001) orientation parallel to the substrate surface. Thickness fringes on the (002) peaks were present at higher substrate temperatures and gave thicknesses of 9 to 16 nm, linearly increasing from 760 C. to 930 C., for a one hour growth. A growth rate of 35 nm/hr was obtained when the source temperature was raised to 85 C., FIG. 5, showing that scalable growth rates are possible, especially knowing the source temperature can be increased up to 210 C., the decomposition temperature of Pt(acac).sub.2.

[0062] Although the HRXRD plot in FIG. 4(a) suggested single crystalline films, the microstructure of the films visualized by AFM proved otherwise. Atomically smooth islands were observed with a decreasing island size as the substrate temperature was decreased. In some cases, the elongated island morphology shown at higher temperatures is commonly attributed to the favorable agglomeration of metals on dielectric materials. In the case of Pt, it has been shown that a transition from 2-D to 3-D growth occurs as substrate temperature is increased due to the increasing capillary forces from the dielectric substrate.

[0063] A similar trend was observed with the larger degree of 3D growth at higher substrate temperatures. At a temperature of 630 C. and below, the film surface consisted of many smaller faceted islands. This can also be observed in the RHEED patterns after growth along the SrTiO.sub.3 [110] azimuth, a spotty pattern occurred from transmission through these faceted islands. As the substrate temperature was increased, RHEED evolved into a streaky pattern due to diffraction from the atomically smooth island surfaces. While not wishing to be bound by any theory, at temperatures of 760 C. and higher, the RHEED patterns looked similar to previously reported patterns in which the additional small streaks were attributed to a superimposed pattern due to the additional small presence of the (110) plane on the surface. Finally, when the substrate temperature was decreased to 400 C., the Pt (002) peak disappeared and the Pt (111) peak appeared, the energetically preferred orientation for Pt.

Example 2

[0064] In this example, the polarization of the substrate was screened while retaining the template structure by growing on a conducting Nb-doped SrTiO.sub.3 (001) substrate. By only changing to a metallic lower electrical boundary condition for film growth, single crystalline atomically smooth platinum films were obtained. A 70 nm platinum film with a single peak in the HRXRD plot is shown in FIG. 5. Steps are seen in the surface from AFM with a step height of one platinum unit cell. A similar RHEED pattern was obtained as those films grown at high substrate temperatures on undoped SrTiO.sub.3 but with more well-defined streaks, attesting to the high quality and smooth surface.

Example 3

[0065] In this example a thicker 70 nm film was grown on SrTiO.sub.3 at an intermediate substrate temperature of 760 C. along with a source temperature of 85 C. to increase the growth rate. Four probe temperature dependent resistivity measurements were performed down to 1.8 K as can be seen in FIG. 5(d). A room temperature resistivity () of 15.1 cm was obtained, slightly larger than the bulk Pt value of 10.6 cm. The Bloch-Grneisen equation was used to fit the resistivity vs temperature behavior and a Debye temperature .sub.D of 232 K was determined, agreeing well with the bulk value of 240 K.

[0066] The residual resistivity ratio (RRR), defined here as (300 K)/(1.8 K), was 27. The RRR is a measure of the crystal quality due to the residual resistivity greatly depending on defects and impurities. The RRR of Pt films grown by the common PVD techniques is plotted against the rough cost/complexity of supplying the metal in FIG. 6.

[0067] Keeping in mind the difference in substrates and film thickness, the Pt film grown using the techniques of the present disclosure had a larger RRR while being simple and relatively cheap to deliver the Pt, i.e. low temperature sublimation in an effusion cell. As the residual resistivity is heavily influenced by impurities, a larger value would be expected to be obtained if a purer Pt(acac).sub.2 source material is used, such as 99.98% Pt(acac).sub.2 which is commercially available.

Example 4

[0068] To show the extent of this technique does not only apply to the simple metal Pt, RuO.sub.2 films were grown on r-plane sapphire, r-Al.sub.2O.sub.3, using a Ru(acac).sub.3 source temperature of 100 C. with varying substrate temperature. The HRXRD plot of FIG. 7(a) shows the single (101) orientation of RuO.sub.2 at all substrate temperatures, from 300 C. to 850 C. Although single phase, films grown at lower substrate temperatures showed a higher degree of crystalline order and structural quality with smooth surfaces mirroring the steps of the substrate (FIG. 7(d)), streaky RHEED patterns (FIGS. 7(a)-7(b)), and FWHM from the (101) rocking curve of around 0.1 (FIG. 7(e)). Increasing the substrate temperature caused over an order of magnitude increase in the FWHM and an increase in the growth rate, from 0.11 to 0.28 nm/min at 300 C. to 650 C. The films grown at 750 C. and 850 C. showed island formation and were too rough to determine thickness from GIXR.

[0069] Resistivity of RuO.sub.2 grown at a substrate temperature of 300 C. was about 5 that of bulk RuO.sub.2, as shown in FIG. 7(f). The resistivity did decrease as thickness was increased but remained relatively constant after 23 nm, still not reaching bulk resistivity. Regardless of substrate temperature and thickness, RRR values were around 2-3 for all films grown on r-Al.sub.2O.sub.3 expect for those grown at 750 C. and 850 C. which were insulating, most likely due to being discontinuous films from the island formation.

Example 5

[0070] RuO.sub.2 films grown on r-Al.sub.2O.sub.3 having larger than bulk resistivity is not too surprising as the substrate has a different lattice size and symmetry which can greatly affect the structural quality of the epitaxial film. With RuO.sub.2 having the ideal rutile structure, a series of films were grown on rutile symmetry TiO.sub.2 substrates with two different orientations and on a rutile in-situ grown SnO.sub.2 film to determine their lattice size and orientation effect on the electrical transport. First, FIG. 8(a) shows the HRXRD plot of these films compared to a RuO.sub.2 grown on r-Al.sub.2O.sub.3. Single phase epitaxial films were formed following the symmetry of the respective substrate. Slight peak shifts are present in all of the films except the one grown on the 35 nm SnO.sub.2 film due to residual strain in the film. By growing on the (101) rutile surface of SnO.sub.2, the bulk room temperature resistivity of RuO.sub.2 was recovered at the small thickness of 10 nm.

[0071] As shown in FIG. 8(b), the (110) and (001) orientations again showed an increased resistivity but not as large as on r-Al.sub.2O.sub.3, attesting to the increased quality when grown on the same symmetry.

[0072] Overall, the present disclosure shows that the solid source MOMBE technique grows high quality RuO.sub.2 films at the low substrate temperature of 300 C. and with bulk-like room temperature resistivity.

EMBODIMENTS

[0073] Embodiment A. A system, comprising: [0074] a vacuum chamber; [0075] a substrate in the vacuum chamber, wherein the substrate comprises a target surface; and [0076] at least one effusion cell in the vacuum chamber, wherein the effusion cell contains a solid metal-organic precursor compound with a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C., and wherein the effusion cell is configured to sublime the solid metal-organic precursor compound at a sublimation temperature greater than about 0 C. and less than about 200 C. such that a stream of metal particles from the solid metal-organic precursor compound that emanate from the effusion cell are directed toward to the target surface of the substrate to form a coating thereon.
Embodiment B. The system of Embodiment A, wherein the sublimation temperature is less than about 100 C.
Embodiment C. The system of Embodiment A, wherein the sublimation temperature is less than about 85 C.
Embodiment D. The system of Embodiment A, wherein the sublimation temperature is about 65 C. to about 85 C.
Embodiment E. The system of any of Embodiments A to D, wherein the solid metal-organic precursor compound comprises a metal chosen from Pt, Ru, Ir, W, and mixtures and combinations thereof.
Embodiment F. The system of Embodiment E, wherein the solid metal-organic precursor compound comprises a -diketonate with a metal chosen from Pt, Ir, Ru, and combinations thereof.
Embodiment G. The system of Embodiment E, wherein the -diketonate is Pt acetylacetonate (Pt(acac).sub.2).
Embodiment H. The system of any of Embodiments A to G, wherein the target surface is heated.
Embodiment I. The system of Embodiment H, wherein the target surface is heated to a temperature of about 400 C. to about 930 C.
Embodiment J. The system of Embodiments H or I, wherein the target surface comprises SrTiO.sub.3.
Embodiment K. The system of Embodiment J, wherein the SrTiO.sub.3 is doped.
Embodiment L. The system of any of Embodiments A to K, further comprising an oxygen source configured to direct a beam of oxygen atoms toward the target surface.
Embodiment M. The system of any of Embodiments A to L, wherein the vacuum chamber is free of a carrier gas.
Embodiment N. The system of any of Embodiments A to M, wherein the vacuum chamber comprises a carrier gas.
Embodiment O. The system of any of Embodiments A to N, wherein vacuum chamber comprises a plurality of effusion chambers.
Embodiment P. The system of any of Embodiments A to O, wherein the coating comprises a thin film.
Embodiment Q. The system of Embodiment P, wherein the thin film comprises Pt.
Embodiment R. A method for making a coating, the method comprising: [0077] subliming at a sublimation temperature of greater than about 0 C. and up to about 200 C. a solid metal-organic precursor compound having a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C. to form a flow of metal particles; and [0078] directing the flow of metal particles toward a target surface to form the coating thereon.
Embodiment S. The method of Embodiment R, wherein the sublimation temperature is less than about 100 C.
Embodiment T. The method of Embodiment R, wherein the sublimation temperature is less than about 85 C.
Embodiment U. The method of Embodiment R, wherein the sublimation temperature is about 65 C. to about 85 C.
Embodiment V. The method of any of Embodiments R to U, wherein the solid metal-organic precursor compound comprises a metal chosen from Pt, Ru, Ir, W, and mixtures and combinations thereof.
Embodiment W. The method of Embodiment V, wherein the solid metal-organic precursor compound comprises a -diketonate with a metal chosen from Pt, Ir, Ru, and combinations thereof.
Embodiment X. The method of Embodiment V, wherein the -diketonate is Pt acetylacetonate (Pt(acac).sub.2).
Embodiment Y. The method of any of Embodiments R to X, wherein the solid metal-organic precursor compound is sublimed in an effusion chamber.
Embodiment Z. The method of Embodiment Y, wherein the effusion chamber is within a vacuum chamber.
Embodiment AA. The method of any of Embodiments R to Z, wherein the solid metal-organic precursor compound is sublimed at below atmospheric pressure.
Embodiment BB. The method of any of Embodiments R to AA, further comprising heating the target surface to a temperature of about 400 C. to about 1000 C.
Embodiment CC. The method of Embodiment BB, wherein the target surface comprises SrTiO.sub.3.
Embodiment DD. The method of Embodiment CC, wherein the SrTiO.sub.3 is doped.
Embodiment EE. The method of any of Embodiments R to DD, further comprising directing a flow of oxygen atoms toward the target surface.
Embodiment FF. The method of any of Embodiments R to EE, wherein the flow of metal particles toward the target surface is unimpeded by a carrier gas.
Embodiment GG. The method of any of Embodiments R to FF, further comprising subliming a plurality of solid metal-organic precursor compounds to form a plurality of streams of metal particles directed toward the substrate.
Embodiment HH. The method of an of Embodiments R to GG, wherein the coating comprises a thin film.
Embodiment II. A metal coating on a substrate, wherein the metal coating is formed from a stream of metal particles derived from subliming at a sublimation temperature of greater than about 0 C. and up to about 200 C. a solid metal-organic precursor compound having a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 300 C.
Embodiment JJ. The metal coating of Embodiment 11, wherein the sublimation temperature is about 65 C. to about 85 C.
Embodiment KK. The metal coating of Embodiments II to JJ, wherein the solid metal-organic precursor compound comprises a metal chosen from Pt, Ru, Ir, W, and mixtures and combinations thereof.
Embodiment LL. The metal coating of Embodiment KK, wherein the solid metal-organic precursor compound comprises a -diketonate with a metal chosen from Pt, Ir, Ru, and combinations thereof.
Embodiment MM. The metal coating of Embodiment LL, wherein the -diketonate is Pt acetylacetonate (Pt(acac).sub.2).
Embodiment NN. The metal coating of any of Embodiments II to MM, wherein the coating comprises Pt.
Embodiment OO. The metal coating of Embodiment NN, wherein the metal coating consists essentially of Pt.
Embodiment PP. The metal coating of any of Embodiments II to OO, wherein the metal coating is a single crystalline Pt film.
Embodiment QQ. The metal coating of Embodiment PP, wherein the Pt film is atomically smooth.
Embodiment RR. The metal coating of Embodiments PP to QQ, wherein the Pt film has a thickness of about 50 nm to about 100 nm.
Embodiment SS. The metal coating of Embodiment RR, wherein the Pt film has a resistivity () at room temperature of greater than about 10 cm.
Embodiment TT. The metal coating of Embodiment RR, wherein the Pt film has a residual resistivity ratio (RRR) of greater than about 25.
Embodiment UU. The metal coating of any of Embodiments II to TT, wherein the solid metal-organic precursor compound is sublimed in an effusion cell.
Embodiment VV. The metal coating of Embodiment UU, wherein the effusion cell is below atmospheric pressure.
Embodiment WW. The metal coating of any of Embodiments II to VV, wherein the metal coating is derived from a combination of the stream of metal particles and a stream of oxygen atoms.
Embodiment XX. A device comprising an electronic component, wherein at least a portion of the electronic component is coated with a metal coating formed from a stream of metal particles derived from subliming at a sublimation temperature of greater than about 0 C. and up to about 200 C. a solid metal-organic precursor compound having a vapor pressure of less than about 10.2 Torr at a temperature of about 25 C. to about 300 C.
Embodiment YY. The device of Embodiment XX, wherein the electronic component is a capacitor.
Embodiment ZZ. A system comprising: [0079] a vacuum chamber; [0080] a substrate in the vacuum chamber, wherein the substrate comprises a target surface; at least one effusion cell in the vacuum chamber, wherein the effusion cell contains a solid metal-organic precursor compound with a vapor pressure of less than about 10.sup.2 Torr at a temperature of about 25 C. to about 250 C., and [0081] a controller configured to operate the effusion cell to sublime the solid metal-organic precursor compound at a sublimation temperature greater than about 0 C. and less than about 200 C. such that a stream of metal particles from the solid metal-organic precursor compound emanate at a predetermined effusion rate from the effusion cell and are directed toward the target surface of the substrate to form a coating thereon.
Embodiment AAA. The system of Embodiment ZZ, wherein the controller is configured to control a temperature of the target surface from about 400 C. to about 1000 C.
Embodiment BBB. The system of Embodiments ZZ to AAA, wherein the vacuum chamber further comprises a source of oxygen atoms, and wherein the controller is configured to control the source of oxygen atoms to provide a stream of oxygen atoms directed toward the substrate such that oxygen is incorporated into the coating at a predetermined rate.

[0082] Various embodiments of the invention have been described. These and other embodiments are within the scope of the following claims.