Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 1 of 27
`
`
`
`
`Exhibit 13
`
`
`
`
`
`
`
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 2 of 27
`
`(19) United States
`(12) Patent Application Publication (io) Pub. No.: US 2004/0259305 Al
`Dec. 23,2004
`(43) Pub. Date:
`Demaray et al.
`
`US 20040259305A1
`
`(54) ENERGY CONVERSION AND STORAGE
`FILMS AND DEVICES BY PHYSICAL VAPOR
`DEPOSITION OF TITANIUM AND TITANIUM
`OXIDES AND SUB-OXIDES
`
`(76) Inventors: Richard E. Demaray, Portola Valley,
`CA (US); Hong Mei Zhang, San Jose,
`CA (US); Mukundan Narasimhan,
`San Jose, CA (US); Vassiliki
`Milonopoulou, San Jose, CA (US)
`
`Correspondence Address:
`FINNEGAN, HENDERSON, FARABOW,
`GARRETT & DUNNER
`LLP
`1300 I STREET, NW
`WASHINGTON, DC 20005 (US)
`
`(21) Appl. No.:
`
`10/851,542
`
`(22) Filed:
`
`May 20, 2004
`
`Related U.S. Application Data
`
`(60) Provisional application No. 60/473,375, filed on May
`23, 2003.
`
`Publication Classification
`
`Int. Cl.7 ............................................. H01L 21/8242
`(51)
`(52) U.S. Cl..............................438/240; 438/685; 438/785
`ABSTRACT
`(57)
`High density oxide films are deposited by a pulsed-DC,
`biased, reactive sputtering process from a titanium contain­
`ing target to form high quality titanium containing oxide
`films. A method of forming a titanium based layer or film
`according to the present invention includes depositing a
`layer of titanium containing oxide by pulsed-DC, biased
`reactive sputtering process on a substrate. In some embodi­
`ments, the layer is Ti02. In some embodiments, the layer is
`a sub-oxide of Titanium. In some embodiments, the layer is
`Τ/Ο,. wherein x is between about 1 and about 4 and y is
`between about 1 and about 7. In some embodiments, the
`layer can be doped with one or more rare-earth ions. Such
`layers are useful in energy and charge storage, and energy
`conversion technologies.
`
`18
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 3 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 1 of 15
`
`US 2004/0259305 Al
`
`54
`
`FIG. 1A
`
`12
`
`FIG. 1B
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 4 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 2 of 15
`
`US 2004/0259305 Al
`
`FIG. 2
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 5 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 3 of 15
`
`US 2004/0259305 Al
`
`102
`
`101
`
`104
`
`102
`
`103
`
`101
`
`SUBSTRATE
`
`FIG. 3A
`
`FIG. 3B
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 6 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 4 of 15
`
`US 2004/0259305 Al
`
`201
`
`103
`
`101
`
`201
`
`102
`
`103
`
`101
`
`FIG. 4A
`
`FIG. 4B
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 7 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 5 of 15
`
`US 2004/0259305 Al
`
`103
`
`102
`
`201
`
`102
`
`103
`
`101
`
`FIG. 5
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 8 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 6 of 15
`
`US 2004/0259305 Al
`
`FIG. 6
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 9 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 7 of 15
`
`US 2004/0259305 Al
`
`FIG. 7
`
`1NV1SN09 0ΙΗ103Ί3Ι0
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 10 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 8 of 15
`
`US 2004/0259305 Al
`
`FIG. 8
`
`1NV1SNOO 91^1031310
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 11 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 9 of 15
`
`US 2004/0259305 Al
`
`0Q 0)
`s
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 12 of 27
`
`Patent Application Publication Dec. 23, 2004 Sheet 10 of 15 US 2004/0259305 Al
`
`FIG. 10
`
`0009
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 13 of 27
`
`Patent Application Publication Dec. 23, 2004 Sheet 11 of 15 US 2004/0259305 Al
`
`^wuj/jd A1ISN3C1 39NVllOVdV9
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 14 of 27
`
`Patent Application Publication Dec. 23, 2004 Sheet 12 of 15 US 2004/0259305 Al
`
`FIG. 12
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 15 of 27
`
`Patent Application Publication Dec. 23, 2004 Sheet 13 of 15 US 2004/0259305 Al
`
`FIG. 13
`
`ZvWO/dlAIV
`
`1.0E-04
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 16 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 14 of 15
`
`US 2004/0259305 Al
`
`[PLM 100: 100]
`PHILIPS
`
`INTENSITY AT A DISCRETE WAVELENGTH
`
`2004 MAR 05 13:37
`
`TIOER-3-SWM
`
`[2-5000A]
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 17 of 27
`
`Patent Application Publication Dec. 23,2004 Sheet 15 of 15
`
`US 2004/0259305 Al
`
`[PLM 100: 100]
`PHILIPS
`
`INTENSITY AT A DISCRETE WAVELENGTH
`
`2004 MAR 08 08:00
`
`TI0ER-3-SWM
`
`[2-5000A]
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 18 of 27
`
`US 2004/0259305 Al
`
`1
`
`Dec. 23, 2004
`
`ENERGY CONVERSION AND STORAGE FILMS
`AND DEVICES BY PHYSICAL VAPOR
`DEPOSITION OF TITANIUM AND TITANIUM
`OXIDES AND SUB-OXIDES
`
`RELATED APPLICATIONS
`[0001] The present invention claims priority to U.S. Pro­
`visional Application Ser. No. 60/473,375, “Energy Conver­
`sion and Storage Devices by Physical Vapor Deposition of
`Titanium Oxides and Sub-Oxides,” by Richard E. Demaray
`and Hong Mei Zhang, filed on May 23, 2003, herein
`incorporated by reference in its entirety.
`
`BACKGROUND 1. Field of the Invention
`[0002] The present invention is related to fabrication of
`thin films for planar energy and charge storage and energy
`conversion and, in particular, thin films deposited of tita­
`nium and titanium oxides, sub oxides, and rare earth doped
`titanium oxides and sub oxides for planar energy and charge
`storage and energy conversion. 2. Discussion of Related Art
`[0003] Currently, titanium oxide layers are not utilized
`commercially in energy storage, charge storage, or energy
`conversion systems because such layers are difficult to
`deposit, difficult to etch, are known to have large concen­
`trations of defects, and have poor insulation properties due
`to a propensity for oxygen deficiency and the diffusion of
`oxygen defects in the layers. Additionally, amorphous titania
`is difficult to deposit due to its low recrystalization tempera­
`ture (about 250° C.), above which the deposited layer is
`often a mixture of crystalline anatase and rutile structures.
`[0004] However, such amorphous titania layers, if they
`can be deposited in sufficient quality, have potential due to
`their high optical index, n~2.7, and their high dielectric
`constant, k less than or equal to about 100. Further, they
`have substantial chemical stability. There are no known
`volatile halides and titania is uniquely resistant to mineral
`acids. Amorphous titania is thought to have the further
`advantage that there are no grain boundary mechanisms for
`electrical breakdown, chemical corrosion, or optical scatter­
`ing. It is also well known that the sub oxides of titanium
`have unique and useful properties. See, e.g., Hayfield,
`RC.S., “Development of a New Material- Monolithic Ti407
`Ebonix Ceramic”, Royal Society Chemistry, ISBN 0-85405-
`984-3, 2002. Titanium monoxide, for example, is a conduc­
`tor with a uniquely stable resistivity with varying tempera­
`ture. Additionally, Ti2O3, which can be pinkish in color, is
`known to have semiconductor type properties. However,
`these materials have not found utilization because of their
`difficult manufacture in films and their susceptibility to
`oxidation. Further, Ti407 demonstrates both useful electrical
`conductivity and unusual resistance to oxidation. Ti407,
`however, is also difficult to fabricate, especially in thin film
`form.
`[0005] Additional to the difficulty of fabricating titanium
`oxide or sub oxide materials in useful thin film form, it also
`has proven difficult to dope these materials with, for
`example, rare earth ions, in useful or uniform concentration.
`[0006] Therefore, utilization of titanium oxide and subox­
`ide films, with or without rare earth doping, has been
`significantly limited by previously available thin film pro­
`cesses. If such films could be deposited, their usefulness in
`
`capacitor, battery, and energy conversion and storage tech­
`nologies would provide for many value-added applications.
`[0007] Current practice for construction of capacitor and
`resistor arrays and for thin film energy storage devices is to
`utilize a conductive substrate or to deposit the metal con­
`ductor or electrode, the resistor layer, and the dielectric
`capacitor films from various material systems. Such material
`systems for vacuum thin films, for example, include copper,
`aluminum, nickel, platinum, chrome, or gold depositions, as
`well as conductive oxides such as ITO, doped zinc oxide, or
`other conducting materials.
`[0008] Materials such as chrome-silicon monoxide or tan­
`talum nitride are known to provide resistive layers with 100
`parts per million or less resistivity change per degree Cen­
`tigrade for operation within typical operating parameters. A
`wide range of dielectric materials such as silica, silicon
`nitride, alumina, or tantalum pentoxide can be utilized for
`the capacitor layer. These materials typically have dielectric
`constants k of less than about twenty four (24). In contrast,
`Ti02 either in the pure rutile phase or in the pure amorphous
`state can demonstrate a dielectric constant as high as 100.
`See, e.g., R. B. van Dover, “Amorphous Lanthanide-Doped
`Ti02 Dielectric Films,” Appl. Phys Lett., Vol. 74, no. 20, p.
`3041-43 (May 17, 1999).
`[0009] It is well known that the dielectric strength of a
`material decreases with increasing value of dielectric con­
`stant k for all dielectric films. A ‘figure of merit’ (FM) is
`therefore obtained by the product of the dielectric constant
`k and the dielectric strength measured in Volts per cm of
`dielectric thickness. Capacitive density of 10,000 to 12,000
`pico Farads /mm2 is very difficult to achieve with present
`conductors and dielectrics. Current practice for reactive
`deposition of titanium oxide has achieved a figure-of-merit,
`FM, of about 50 (k MV/cm). See J.-Y. Kim et al., “Fre­
`quency-Dependent Pulsed Direct Current Magnetron Sput­
`tering of Titanium Oxide Films,” J. Vac. Sci. Technol. A
`19(2), Mar/Apr 2001.
`[0010] Therefore, there is an ongoing need for titanium
`oxide and titanium sub-oxide layers, and rare-earth doped
`titanium oxide and titanium sub-oxide layers, for various
`applications.
`
`SUMMARY
`[0011] In accordance with the present invention, high
`density oxide films are deposited by a pulsed-DC, biased,
`reactive sputtering process from a titanium containing tar­
`get. A method of forming a titanium based layer or film
`according to the present invention includes depositing a
`layer of titanium containing oxide by pulsed-DC, biased
`reactive sputtering process on a substrate. In some embodi­
`ments, the layer is Ti02. In some embodiments, the layer is
`a sub-oxide of Titanium. In some embodiments, the layer is
`1/0,. wherein x is between about 1 and about 4 and y is
`between about 1 and about 7.
`[0012] In some embodiments of the invention, the figure
`of merit of the layer is greater than 50. In some embodiments
`of the invention, the layer can be deposited between con­
`ducting layers to form a capacitor. In some embodiments of
`the invention, the layer includes at least one rare-earth ion.
`In some embodiments of the invention, the at least one
`rare-earth ion includes erbium. In some embodiments of the
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 19 of 27
`
`US 2004/0259305 Al
`
`2
`
`Dec. 23, 2004
`
`invention, the erbium doped layer can be deposited between
`conducting layers to form a light-emitting device. In some
`embodiments of the invention, the erbium doped layer can
`be an optically active layer deposited on a light-emitting
`device. In some embodiments of the invention, the layer can
`be a protective layer. In some embodiments, the protective
`layer can be a catalytic layer.
`[0013] In some embodiments of the invention, the layer
`and a Ti02 layer can be deposited between conducting layers
`to form a capacitor with decreased roll-off characteristics
`with decreasing thickness of the Ti02 layer. In some embodi­
`ments, the Ti02 layer can be a layer deposited according to
`some embodiments of the present invention.
`[0014] These and other embodiments of the present inven­
`tion are further discussed below with reference to the
`following figures.
`
`SHORT DESCRIPTION OF THE FIGURES
`[0015] FIGS. 1A and IB illustrate a pulsed-DC biased
`reactive ion deposition apparatus that can be utilized in the
`deposition according to the present invention.
`[0016] FIG. 2 shows an example of a target that can be
`utilized in the reactor illustrated in FIGS. 1A and IB.
`[0017] FIGS. 3A and 3B illustrate various configurations
`of layers according to embodiments of the present invention.
`[0018] FIGS. 4A and 4B illustrate further various con­
`figurations of layers according to embodiments of the
`present invention.
`[0019] FIG. 5 shows another layer structure involving one
`or more layers according to the present invention.
`[0020] FIG. 6 shows a transistor gate with a TiOy layer
`according to the present invention.
`[0021] FIG. 7 illustrates the roll-off of the dielectric
`constant with decreasing film thickness.
`[0022] FIG. 8 illustrates data points from a bottom elec­
`trode that helps reduce or eliminate the roll-off illustrated in
`FIG. 7.
`[0023] FIGS. 9A and 9B illustrate an SEM cross-section
`of a Ti407 target obtained from Ebonex™ and an SEM cross
`section of the Ti4O68 film deposited from the Ebonex™
`target according to the present invention.
`[0024] FIG. 10 shows the industry standard of thin-film
`capacitor performance in comparison with layers according
`to some embodiments of the present invention.
`[0025] FIG. 11 shows the performance of various thin
`films deposited according to the present invention in a
`capacitor structure.
`[0026] FIG. 12 shows a cross-section TEM and diffraction
`pattern amorphous and crystalline layers of Ti02 on n++
`wafers.
`[0027] FIG. 13 shows a comparison of the leakage current
`for Ti02 films according to embodiments of the present
`invention with and without erbium ion doping.
`[0028] FIGS. 14A and 14B show a photoluminescence
`signal measured from a 5000 A layer of 10% erbium
`containing Ti02 deposited from a 10% erbium doped TiO
`
`conductive target and a photoluminescence signal measured
`from the same layer after a 30 minute 250° C. anneal.
`[0029] In the figures, elements having the same designa­
`tion have the same or similar functions.
`
`DETAILED DESCRIPTION
`[0030] Miniaturization is driving the form factor of por­
`table electronic components. Thin film dielectrics with high
`dielectric constants and breakdown strengths allow produc­
`tion of high density capacitor arrays for mobile communi­
`cations devices and on-chip high-dielectric capacitors for
`advanced CMOS processes. Thick film dielectrics for high
`energy storage capacitors allow production of portable
`power devices.
`[0031] Some embodiments of films deposited according to
`the present invention have a combination of high dielectric
`and high breakdown voltages. Newly developed electrode
`materials allow the production of very thin films with high
`capacitance density. The combination of high dielectric and
`high breakdown voltages produce thick films with new
`levels of available energy storage according to E=% CV2.
`[0032] Deposition of materials by pulsed-DC biased reac­
`tive ion deposition is described in U.S. patent application
`Ser. No. 10/101863, entitled “Biased Pulse DC Reactive
`Sputtering of Oxide Films,” to Hongmei Zhang, et al., filed
`on Mar. 16, 2002. Preparation of targets is described in U.S.
`patent application Ser. No. 10/101,341, entitled “Rare-Earth
`Pre-Alloyed PVD Targets for Dielectric Planar Applica­
`tions,” to Vassiliki Milonopoulou, et al., filed on Mar. 16,
`2002. U.S. patent application Ser. No. 10/101863 and U.S.
`patent application Ser. No. 10/101,341 are each assigned to
`the same assignee as is the present disclosure and each is
`incorporated herein in their entirety. Additionally, deposition
`of materials is further described in U.S. Pat. No. 6,506,289,
`which is also herein incorporated by reference in its entirety.
`[0033] FIG. 1A shows a schematic of a reactor apparatus
`10 for sputtering of material from a target 12 according to
`the present invention. In some embodiments, apparatus 10
`may, for example, be adapted from an AKT-1600 PVD
`(400x500 mm substrate size) system from Applied Komatsu
`or an AKT-4300 (600x720 mm substrate size) system from
`Applied Komatsu, Santa Clara, Calif. The AKT-1600 reac­
`tor, for example, has three deposition chambers connected
`by a vacuum transport chamber. These AKT reactors can be
`modified such that pulsed DC (PDC) power is supplied to
`the target and RF power is supplied to the substrate during
`deposition of a material film. The PDC power supply 14 can
`be protected from RF bias power 18 by use of a filter 15
`coupled between PDC power supply 14 and target 12.
`[0034] Apparatus 10 includes a target 12 which is electri­
`cally coupled through a filter 15 to a pulsed DC power
`supply 14. In some embodiments, target 12 is a wide area
`sputter source target, which provides material to be depos­
`ited on substrate 16. Substrate 16 is positioned parallel to
`and opposite target 12. Target 12 functions as a cathode
`when power is applied to it and is equivalently termed a
`cathode. Application of power to target 12 creates a plasma
`53. Substrate 16 is capacitively coupled to an electrode 17
`through an insulator 54. Electrode 17 can be coupled to an
`RF power supply 18. Magnet 20 is scanned across the top of
`target 12.
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 20 of 27
`
`US 2004/0259305 Al
`
`3
`
`Dec. 23, 2004
`
`[0035] For pulsed reactive de magnetron sputtering, as
`performed by apparatus 10, the polarity of the power sup­
`plied to target 12 by power supply 14 oscillates between
`negative and positive potentials. During the positive period,
`the insulating layer on the surface of target 12 is discharged
`and arcing is prevented. To obtain arc free deposition, the
`pulsing frequency exceeds a critical frequency that depends
`on target material, cathode current and reverse time. High
`quality oxide films can be made using reactive pulsed DC
`magnetron sputtering in apparatus 10.
`[0036] Pulsed DC power supply 14 can be any pulsed DC
`power supply, for example an AE Pinnacle plus 10K by
`Advanced Energy, Inc. With this example supply, up to 10
`kW of pulsed DC power can be supplied at a frequency of
`between 0 and 350 KHz. In some embodiments, the reverse
`voltage is 10% of the negative target voltage. Utilization of
`other power supplies will lead to different power character­
`istics, frequency characteristics, and reverse voltage per­
`centages. The reverse time on this embodiment of power
`supply 14 can be adjusted to between 0 and 5 f/s.
`[0037] Filter 15 prevents the bias power from power
`supply 18 from coupling into pulsed DC power supply 14.
`In some embodiments, power supply 18 can be a 2 MHz RF
`power supply, for example a Nova-25 power supply made by
`ENI, Colorado Springs, Colo.
`[0038] Therefore, filter 15 can be a 2 MHz band sinusoidal
`rejection filter. In some embodiments, the bandwidth of the
`filter can be approximately 100 kHz. Filter 15, therefore,
`prevents the 2 MHz power from the bias to substrate 16 from
`damaging power supply 18.
`[0039] However, both RF sputtered and pulsed DC sput­
`tered films are not fully dense and may typically have
`columnar structures. These columnar structures are detri­
`mental to thin film applications. By applying a RF bias on
`wafer 16 during deposition, the deposited film can be
`densified by energetic ion bombardment and the columnar
`structure can be substantially eliminated or completely
`eliminated.
`[0040] In the AKT-1600 based system, for example, target
`12 can have an active size of about 675.70x582.48 by 4 mm
`in order to deposit films on substrate 16 that have dimension
`about 400x500 mm. The temperature of substrate 16 can be
`held at between -50C and 500C by introduction of back-side
`gas in a physical or electrostatic clamping of the substrate,
`thermo-electric cooling, electrical heating, or other methods
`of active temperature control. In FIG. 1A, a temperature
`controller 22 is shown to control the temperature of substrate
`16. The distance between target 12 and substrate 16 can be
`between about 3 and about 9 cm. Process gas can be inserted
`into the chamber of apparatus 10 at a rate up to about 200
`seem while the pressure in the chamber of apparatus 10 can
`be held at between about 0.7 and 6 millitorr. Magnet 20
`provides a magnetic field of strength between about 400 and
`about 600 Gauss directed in the plane of target 12 and is
`moved across target 12 at a rate of less than about 20-30
`sec/scan. In some embodiments utilizing the AKT 1600
`reactor, magnet 20 can be a race-track shaped magnet with
`dimension about 150 mm by 600 mm.
`[0041] FIG. 2 illustrates an example of target 12. A film
`deposited on a substrate positioned on carrier sheet 17
`directly opposed to region 52 of target 12 has good thickness
`
`uniformity. Region 52 is the region shown in FIG. IB that
`is exposed to a uniform plasma condition. In some imple­
`mentations, carrier 17 can be coextensive with region 52.
`Region 24 shown in FIG. 2 indicates the area below which
`both physically and chemically uniform deposition can be
`achieved, where physical and chemical uniformity provide
`refractive index uniformity, for example. FIG. 2 indicates
`that region 52 of target 12 that provides thickness uniformity
`is, in general, larger than region 24 of target 12 providing
`thickness and chemical uniformity. In optimized processes,
`however, regions 52 and 24 may be coextensive.
`[0042] In some embodiments, magnet 20 extends beyond
`area 52 in one direction, the Y direction in FIG. 2, so that
`scanning is necessary in only one direction, the X direction,
`to provide a time averaged uniform magnetic field. As
`shown in FIGS. 1A and IB, magnet 20 can be scanned over
`the entire extent of target 12, which is larger than region 52
`of uniform sputter erosion. Magnet 20 is moved in a plane
`parallel to the plane of target 12.
`[0043] The combination of a uniform target 12 with a
`target area 52 larger than the area of substrate 16 can provide
`films of highly uniform thickness. Further, the material
`properties of the film deposited can be highly uniform. The
`conditions of sputtering at the surface of target 12, such as
`the uniformity of erosion, the average temperature of the
`plasma at the target surface and the equilibration of the
`target surface with the gas phase ambient of the process are
`uniform over a region which is greater than or equal to the
`region to be coated with a uniform film thickness. In
`addition, the region of uniform film thickness is greater than
`or equal to the region of the film which is to have highly
`uniform optical properties such as index of refraction, den­
`sity, transmission, or absorptivity.
`[0044] Target 12 can be formed of any materials, but is
`typically metallic materials such as, for example, combina­
`tions of In and Sn. Therefore, in some embodiments, target
`12 includes a metallic target material formed from interme­
`tallic compounds of optical elements such as Si, Al, Er and
`Yb. Additionally, target 12 can be formed, for example, from
`materials such as La, Yt, Ag, Au, and Eu. To form optically
`active films on substrate 16, target 12 can include rare-earth
`ions. In some embodiments of target 12 with rare earth ions,
`the rare earth ions can be pre-alloyed with the metallic host
`components to form intermetallics. See U.S. application Ser.
`No. 10/101,341.
`[0045] In several embodiments of the invention, material
`tiles are formed. These tiles can be mounted on a backing
`plate to form a target for apparatus 10. A wide area sputter
`cathode target can be formed from a close packed array of
`smaller tiles. Target 12, therefore, may include any number
`of tiles, for example between 2 to 20 individual tiles. Tiles
`are finished to a size so as to provide a margin of non­
`contact, tile to tile, less than about 0.010" to about 0.020" or
`less than half a millimeter so as to eliminate plasma pro­
`cesses that may occur between adjacent ones of the tiles. The
`distance between the tiles of target 12 and the dark space
`anode or ground shield 19 in FIG. IB can be somewhat
`larger so as to provide non contact assembly or provide for
`thermal expansion tolerance during processing, chamber
`conditioning, or operation.
`[0046] As shown in FIG. IB, a uniform plasma condition
`can be created in the region between target 12 and substrate
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 21 of 27
`
`US 2004/0259305 Al
`
`4
`
`Dec. 23, 2004
`
`16 in a region overlying substrate 16. A plasma 53 can be
`created in region 51, which extends under the entire target
`12. A central region 52 of target 12, can experience a
`condition of uniform sputter erosion. As discussed further
`below, a layer deposited on a substrate placed anywhere
`below central region 52 can then be uniform in thickness and
`other properties (i.e., dielectric, optical index, or material
`concentrations). In addition, region 52 in which deposition
`provides uniformity of deposited film can be larger than the
`area in which the deposition provides a film with uniform
`physical or optical properties such as chemical composition
`or index of refraction. In some embodiments, target 12 is
`substantially planar in order to provide uniformity in the film
`deposited on substrate 16. In practice, planarity of target 12
`can mean that all portions of the target surface in region 52
`are within a few millimeters of a planar surface, and can be
`typically within 0.5 mm of a planar surface.
`[0047] FIG. 3A illustrates deposition of a layer 102
`according to the present invention deposited on a substrate
`101. In some embodiments, layer 102 can be a conducting
`protective layer of TiOy. FIG. 3B shows a first layer 102
`according to the present invention deposited over a second
`layer 103, which can also be a layer according to some
`embodiments of the present invention. In some embodi­
`ments, first layer 102 can be a conducting protective layer
`and second layer 103 can be a titanium or other conducting
`layer. Layer 103 is deposited on substrate 101.
`[0048] The fabrication of high density capacitor and resis­
`tor arrays as well as high energy storage solid state devices
`can be accomplished with embodiments of processes
`according to the present invention on a wide variety of
`substrates such as silicon wafers or glass or plastic sheets at
`low temperature and over wide area. With reference to FIG.
`3B, layer 102 can be an amorphous film of Ti02, which is
`deposited by a process such as that described in U.S.
`application Ser. No. 10/101,341. Utilization or formation of
`a conducting layer 103 such as TiO or Ti407 between a
`conducting layer of titanium, which is substrate 101, and the
`dielectric Ti02 layer 102 is shown in the present invention
`to substantially reduce or eliminate the ‘roll off’ of the
`dielectric constant k with decreasing film thickness below
`about 1000 Angstroms. Consequently, capacitors fabricated
`from titanium on low temperature substrates result in high
`value planar capacitors and capacitor arrays with very high
`capacitive density and low electrical leakage. Such electrical
`arrays are useful for shielding and filtering and buffering
`high frequency and may be used in stationary as well as in
`portable electronic devices.
`[0049] In particular, the low temperature deposition of
`amorphous titania capacitors provides for the fabrication of
`integrated passive electronic circuits on plastic and glass. It
`also provides for the integration of such devices on other
`electronic devices and arrays at low temperature.
`[0050] Similarly, a conducting layer of TiO or Ti407 as
`layer 103 in FIG. 3B, deposited between a conducting layer
`of titanium as layer 101 and a layer of titania as layer 102
`of FIG. 3B can be deposited so as to provide an increase in
`the surface smoothness by planarization of the titanium in
`layer 101 or other metallurgical conductive substrate layer
`101 of FIG. 3B. Consequently, roughness or asperity based
`defects can be minimized or eliminated. As an example,
`charge injection from a metallurgical electrode can be
`
`decreased at the interface with a dielectric. The titanium
`based dielectric layer can be formed on a smooth conducting
`oxide layer, which according to some theories can prevent
`charge depletion of the high k dielectric layer, decrease point
`charge accumulation and support dipole formation at the
`conductor-dielectric interface, sometimes referred to as
`dipole coupling. These features are important to prevent the
`roll-off of the dielectric strength of the dielectric layer as the
`layer thickness is decreased below about 1000 A. It is
`consequently useful in the formation of thin layers having
`high capacitive value.
`[0051] A thick film of dielectric material may be deposited
`having a high dielectric strength for the storage of electrical
`energy. Such energy is well known to increases with the
`square of the applied Voltage. For example, in FIG. 3B layer
`102 can be a thick layer of dielectric according to the present
`invention. Layer 104 in FIG. 3B, then, can be a conducting
`layer deposited on layer 102 while layer 103 is a conducting
`layer deposited between a substrate 101 and layer 102 to
`form a capacitor. As the dielectric strength of the amorphous
`dielectric layer of layer 102 increases in proportion to it’s
`thickness, the energy storage also increases effectively as the
`square of the thickness. It is shown that both record capaci­
`tance density and electrical energy storage density result for
`films according to the present invention. For thick film
`applications, smoothing of the metallurgical electrode by a
`conductive sub-oxide can decrease leakage at the interface
`in high voltage applications.
`[0052] Protective conductive sub-oxide films of titanium
`can also be deposited on conductive and insulating sub­
`strates to protect them from harmful chemical attack while
`acting as conducting layers. For example, as illustrated in
`FIG. 3A layer 102 can be a protective conductive sub-oxide
`film deposited on substrate 101. These layers can be used to
`protect an electrode, which can be substrate 101, from
`oxidation in the gas phase and in the liquid phase as well as
`the solid phase. Examples of such applications include
`electrolytic energy storage or as an active electrode surface
`for catalytic reactions and energy conversion such as in the
`oxygen-hydrogen fuel cell. Transparent oxides and semi­
`transparent sub-oxides can be deposited sequentially so that
`the conducting sub-oxides are protected by the transparent
`non-conducting oxides for purposes of photovoltaic or elec-
`trochromic energy conversion devices. It is well known that
`organic based photovoltaic cells are enhanced by the pres­
`ence of titania in the organic absorbing layer. Layers accord­
`ing to the present invention can be utilized both for the
`conductivity of electricity, the enhancement of the organic
`absorber, as well as the overall protection of the device.
`[0053] Ti02 layers, for example, can photocatylitically
`produce ozone in the presence of sunlight. However, in the
`course of such activity, the Ti02 layer can build up a fixed
`charge. Absent a metallurgical conductor, as shown in FIG.
`3B layer 102 can be a catalytic oxide while layer 103 can be
`a conducting suboxide while substrate 101 is a dielectric
`substrate such as glass or plastic and layer 104 is absent. In
`such a two-layer device, where the oxide is provided on the
`surface of the sub-oxide, the sub-oxide can form an elec­
`trode so that electric charge can be conducted to the oxide
`layer for enhanced photochemical photalysis such as in an
`AC device, or for the purpose of charge dissipation.
`[0054] Protective conductive sub-oxide films of titanium
`can also be deposited on conductive and insulating sub­
`
`

`

`Case 6:20-cv-00636-ADA Document 48-16 Filed 02/16/21 Page 22 of 27
`
`US 2004/0259305 Al
`
`5
`
`Dec. 23, 2004
`
`strates to protect them from harmful chemical attack while
`acting as conducting layers for electrolytic energy storage or
`as an active electrode for cataly