JP2012517717A - Sintered nanopore electrical capacitor, electrochemical capacitor and battery, and manufacturing method thereof - Google Patents

Abstract

  The present invention relates generally to the field of continuous surface chemistry. More specifically, the present invention relates to products and methods for manufacturing the products that use atomic layer deposition (“ALD”) to deposit one or more materials on a surface. ALD has the capability of high quality, defect free film deposition with few molecular layers. The present invention, in various embodiments, includes methods for producing electrical components such as batteries, capacitors and electrochemical capacitors by ALD, and products produced by those methods.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of US patent application Ser. No. 12 / 370,394, filed on Feb. 12, 2009, both of which are dated Feb. 13, 2008. Claims the benefit of US Provisional Patent Applications Nos. 61 / 028,383 and 61 / 028,402, all of which are hereby incorporated by reference in their entirety. This application is also a benefit of US Provisional Patent Application No. 61 / 259,550 filed on November 9, 2009 and United States Provisional Patent Application No. 61 / 262,851 filed on November 19, 2009. Both of which are incorporated herein by reference in their entirety.

  The present invention relates generally to the field of continuous surface chemistry. More specifically, the present invention relates to products and methods for manufacturing the products that use atomic layer deposition (“ALD”) to deposit one or more materials on a surface.

  ALD is a thin film deposition technique based on the continuous use of gas phase chemical processes. ALD is of high quality and has the capability of molecular scale film deposition. ALD has been used for about 40 years so far, for details related to ALD technology, the entire contents of which are incorporated herein by reference in their entirety, US Pat. No. 4,058,430, US Pat. See No. 4,413,022, http://en.wikipedia.org/wiki/Atomic_Layer_Deposition and http://www.colorado.edu/chemistry/GeorgeResearchGroup/intro/IntroALD.pdf. ALD manufacturing technology has been developed to a high level and deposition equipment is available from several companies. See, for example, www.picosun.com, www.beneq.com, www.oxford-instruments.com, www.cambridgenanotech.com, www.sundewtech.com, all of which are incorporated herein by reference in their entirety. .

  Chemical vapor deposition (“CVD”) processes are useful for forming a layer of material, such as an electrode, on a substrate surface. However, the non-uniformity of the layer deposited on the substrate can lead to void and thickness variations, thereby rendering the electrode or other electrical component inoperable. In addition, CVD covers the exposed surface of the substrate, but ALD is invasive and conformal to both the exposed and hidden surfaces due to the self-limiting nature of the ALD process, and even A layer of thickness will be coated. Such CVD-like features are also found in vapor deposition and sputtering. Some of these features can be used as useful when a coating is only needed on the exposed surface.

  The current technology for capacitors with high specific capacity (defined herein as the product of microfarads and volts per cubic millimeter) is aluminum and tantalum electrolytic capacitors, http: //en.wikipedia/ See org / wiki / Electrolytic_capacitor. For example, the size of a 10V, 10 μF, tantalum electrolytic capacitor for surface mount applications is approximately 2 × 2 × 3.5 mm 3. The specific capacity of such an electrolytic capacitor is 7.1 V μF / mm 3, which will have a leakage current of about 1 μA after about 2 minutes of application of the rated voltage. tan δ is 0.06. This electrolytic capacitor should withstand about 2000 hours at 85 ° C. and rated voltage. In short, electrolytic capacitors are severely limited in their applications due to short lifetimes (especially at high temperatures), high series resistance, energy loss due to ripple currents that cause heating, inability to use in AC applications, harmful failure modes (Conducting electrolyte diffusion), limited operating temperature range, high leakage current, capacitance depending on how long the capacitor has been under applied voltage, etc.

  Attempts have been made to construct capacitors that are deposited by ALD on anode Al with nanopores. See “Nanotubular metal-insulator-metal capacitor arrays for energy storage”, Parag Banerjee and others, Nature Nanotechnology, VOL 4, May 2009, page 292, which is incorporated herein in its entirety. However, such a design lacks a solution that allows this component to be connected to electrical wiring with a fairly low resistance.

  ALD fabrication gates and capacitors in semiconductor applications demonstrate advantages over other known fabrication methods. Some ALD films are specially free of defects, down to 1-2 molecular layers, free of stress, and free of pinholes. This unique feature is useful for depositing gate and capacitor dielectrics, diffusion barriers and seed layers. For general discussion, see http://www.semiconductor.net/article/279085-IMEC_Tips_10_nm_Options_at_Tech_Forum.php, http://www.semiconductor.net/article/, which is incorporated herein by reference in its entirety. 206893-ALD_PVD_Barrier_Reduces_RC_and_Improves_Reliability.php, http://www.semiconductor.net/article/358034-High_Power_Transistors_Emerge_at_CEATEC.php and `` Needs for Next Generation Memory and Enabling Solutions Based on Advanced Vaporizer ALD Technology '', Prof. Zia Kared See International Conference on Atomic Layer deposition, July 2009, Monterey, CA, USA, page 57.

  Electrochemical capacitors (also known as electric double layer capacitors or supercapacitors) are used when large capacitances are needed and take advantage of the cell's ion flow to store charge. Electrochemical capacitors have a large number, typically millions of charge / discharge cycles, can have fast charge / discharge times, but can store less energy than batteries.

  Electric batteries use chemical compounds to store energy. See, for example, `` Batteries and electrochemical capacitors '', Hector D. Abruiio and others, Physics Today, December 2008, page 43, and `` Solid-state microscale lithium batteries prepared with microfabrication, all incorporated herein by reference in their entirety. processes ", Jie Song and others, 2009, J. Micromech. Microeng. 19 045004 (6pp).

  The term “battery” as used herein generally refers to an electric battery unless explicitly stated otherwise. The chemical reaction generates a flow of ions in the battery and a current flow out of the battery. Some batteries (secondary cells) can be charged by applying a current that causes energy storage in the flow of ions and chemical bonds. Most batteries have the limitation that the number of charge / discharge cycles is limited to only a few thousand cycles, the charge / discharge time is relatively slow, and most batteries generate heat during operation.

  There has been a considerable amount of research on materials that can be applied as anodes, cathodes, electrolytes and separators for batteries. In advanced designs, one material is used as both an electrolyte and a separator and is referred to as a fast ionic conductor, solid electrolyte or superionic conductor. The term “solid electrolyte” will be used herein.

  However, batteries, capacitors, electrochemical capacitors and other components that overcome the aforementioned problems and also make components that are more efficient due to reduced size, better performance parameters and improved reliability There is still a need for improved methods of manufacturing electrical components such as. Various embodiments of the present invention address these needs.

U.S. Pat. No. 4,058,430 US Pat. No. 4,413,022 US Pat. No. 3,574,681 US Pat. No. 3,850,762 US Pat. No. 4,687,551 US Pat. No. 5,112,449 US Pat. No. 6,838,297

Internet <URL: http://en.wikipedia.org/wiki/Atomic_Layer_Deposition> Internet <URL: http://www.colorado.edu/chemistry/GeorgeResearchGroup/intro/IntroALD.pdf> Internet <URL: www.picosun.com> Internet <URL: www.beneq.com> Internet <URL: www.oxford-instruments.com> Internet <URL: www.cambridgenanotech.com> Internet <URL: www.sundewtech.com> Internet <URL: http://en.wikipedia.org/wiki/Electrolytic_capacitor> Parag Banerjee, `` Nanotubular metal-insulator-metal capacitor arrays for energy storage '', Nature Nanotechnology, May 2009, VOL 4, 292 pages Internet <URL: http: //www.semiconductor.net/article/279085-IMEC_Tips_10_nm_Options_at_Tech_Forum.php> Internet <URL: http://www.semiconductor.net/article/206893-ALD_PVD_Barrier_Reduces_RC_and_Improves_Reliability.php> Internet <URL: http: //www.semiconductor.net/article/358034-High_Power_Transistors_Emerge_at_CEATEC.php> Zia Karim, `` Needs for Next Generation Memory and Enabling Solutions Based on Advanced Vaporizer ALD Technology '', Proceedings of the 9th International Conference on Atomic Layer deposition, July 2009, Monterey, CA, USA, p. 57 Hector D. Abruiio, “Batteries and electrochemical capacitors”, Physics Today, December 2008, p. 43 Jie Song, "Solid-state microscale lithium batteries prepared with microfabrication processes", 2009, J. Micromech. Microeng. 19 045004 (6pp) Internet <URL: http://www.whatman.com/PRODAnoporeInorganicMembranes.aspx> Internet <URL: http://www.2spi.com/catalog/spec_prep/filter2.shtml>

In one embodiment of the invention,
A first electrode formed of a sintered structure made of hardly oxidized metal particles having a filling rate of less than 100%;
A dielectric layer formed by ALD, substantially surrounding the first electrode;
An insulator formed on the exposed surface of the sintered structure;
A second electrode formed in the remaining volume to fully or partially supplement the first electrode and the dielectric layer;
An electrical component is provided that includes a sintered structure and a first terminal and a second terminal disposed in electrical connection with the second electrode, respectively.

  These sintered capacitors have a completely monolithic structure, no leakage, low series resistance and inductance, long life at high temperature, and without causing damage to surrounding electronics in case of failure, Complete AC operation is possible. A sintered capacitor manufactured according to this embodiment has, by way of example and not limitation, a specific capacity of 25 V μF / mm 3, which is 3.5 times higher than a tantalum capacitor and 35 times higher than an aluminum capacitor.

  According to yet another embodiment, an electrochemical capacitor or battery is provided as in the previous embodiment, but the dielectric is replaced with an anode material, a cathode material and a solid electrolyte material. Primarily due to the fact that the distance that ions need to travel between the cathode and anode is on the order of nanometers compared to a few millimeters or a tenth of a few millimeters with conventional such components. Thus, these electrochemical capacitors and batteries will have improved performance compared to conventional electrochemical capacitors or batteries.

  According to yet another embodiment, an electrochemical capacitor or battery is provided as in the previous embodiment, but the second electrode is omitted and either the cathode or the anode, both the first electrode Farther away, it will carry the current to the second terminal.

According to another embodiment of the present invention, a method of manufacturing an electrical component is provided, the method comprising:
Providing a first electrode formed of a sintered structure made of metal particles having a fill factor of less than 100% that is hardly oxidized;
Soldering, brazing or other techniques to solder the first terminal to the sintered structure to form a mechanical and electrical connection between the first terminal and the first electrode; ,
Depositing a dielectric layer using ALD, the dielectric layer substantially surrounding the first electrode;
Attaching an insulator formed on the exposed surface of the structure (note that this step and the previous step can be reversed);
Providing a second electrode formed in part or all of the remaining volume to supplement the first electrode and the dielectric layer;
Soldering, brazing or other technique to connect a second terminal disposed in electrical connection with the second electrode.

  According to yet another embodiment, a method of manufacturing an electrochemical capacitor or battery is provided as in the previous embodiment, but the step of depositing the dielectric is performed using ALD as the anode material, solid electrolyte. Replacing the step of depositing the material and cathode material in this order or in the reverse order, the step of attaching the insulator is performed before or after the step of depositing the solid electrolyte.

  According to yet another embodiment, a method of manufacturing an electrochemical capacitor or battery is provided as in the previous embodiment, but the step of depositing the second electrode is omitted and either a cathode or anode However, both are farther from the first electrode, but will carry current to the second terminal.

According to yet another embodiment,
A scaffold having a plurality of pores therein, wherein the at least one pore traverses the scaffold from a first surface to a second surface;
A first conductor deposited on the surface of the scaffold including on the inner surface of the plurality of pores;
A first conductive surface at a first surface in electrical contact with the first conductor;
A first terminal that is brazed or soldered to a first conductive surface;
A dielectric deposited on the surface of the first conductor, including on the inner surfaces of the plurality of pores;
An insulator attached to the exposed surface of the scaffold;
A second conductor deposited on the surface of the dielectric including on the inner surfaces of the plurality of pores;
A second conductive surface at a second surface, wherein the second conductive surface is in electrical contact with the second conductor;
A capacitor is provided having a second terminal that is brazed or soldered to a second conductive surface.

  According to yet another embodiment, an electrochemical capacitor or battery is provided as in the previous embodiment, but the dielectric is replaced with an anode material, a solid electrolyte material and a cathode material.

  According to yet another embodiment, an electrochemical capacitor or battery is provided as in the previous embodiment, but the first conductor and the second conductor are omitted, and the anode and cathode carry the current. Carry to the first conductive surface and the second conductive surface, respectively, or to the second conductive surface and the first conductive surface, respectively.

According to yet another embodiment, a method of manufacturing a capacitor is provided, the method comprising:
Providing a scaffold having a plurality of pores therein, wherein the at least one pore traverses the scaffold from a first surface to a second surface;
Using ALD to deposit a first conductor on the surface of the scaffold, including on the inner surface of the plurality of pores;
Using CVD, vapor deposition, sputtering or another technique to place a first conductive surface in electrical contact with the conductor, typically on the first side of the scaffold but generally not in the pores;
Brazing or soldering the first terminal to the first conductive surface;
Depositing a dielectric on the surface of the first conductor using ALD, including on the inner surfaces of the plurality of pores;
Attaching insulators to the exposed surface of the scaffold (note that this step and the previous step can be replaced with the same performance of the final part);
Using ALD to deposit a second conductor on the surface of the dielectric, including on the inner surfaces of the plurality of pores;
Placing a second conductive surface on the second surface using CVD, vapor deposition, sputtering or another technique, wherein the second conductive surface is in electrical contact with the second conductor; When,
Brazing or soldering the second terminal to the second conductive surface.

  According to yet another embodiment, a method of manufacturing an electrochemical capacitor or battery is provided as in the previous embodiment, but the step of depositing the dielectric is performed using ALD as the anode material, solid electrolyte. It is replaced by a step of depositing the material and cathode material in this order or in the reverse order. The step of attaching the insulator will be performed before or after the step of depositing the solid electrolyte.

  According to yet another embodiment, a method of manufacturing an electrochemical capacitor or battery is provided as in the previous embodiment, but using ALD to deposit a first conductor and using ALD. The step of depositing the second conductor is omitted.

According to yet another embodiment,
A perforated scaffold having a plurality of pores, wherein the at least one pore traverses the scaffold from a first surface to a second surface;
Two or more layers of conductive material deposited on the scaffold and substantially covering all surfaces of the pores in the scaffold, wherein the two layers of conductive material are not in direct electrical contact with each other Two or more layers of
A first contact deposited on the first surface;
An electrical component is provided that includes a second contact deposited on the second surface.

  As an optional addition to the above, a first terminal attached to the first contact may be provided, and a second terminal attached to the second contact may be provided.

According to yet another embodiment,
A perforated scaffold having a plurality of pores, wherein the at least one pore traverses the scaffold from a first surface to a second surface;
At least one layer of anode material that substantially covers all surfaces of the scaffold including in the pores of the scaffold;
At least one layer of solid electrolyte material that substantially covers all surfaces of the scaffold including in the pores of the scaffold;
At least one layer of cathode material that substantially covers all surfaces of the scaffold, including in the pores of the scaffold;
A first contact disposed on the first surface;
A second contact disposed on the second surface;
An electrical component is provided that includes an insulating material that separates the anode from the cathode at the outer surface of the scaffold, all layers being deposited on the scaffold and substantially covering all surfaces of the pores within the scaffold. .

  As used herein, the term “substantially covers all surfaces” generally means that the entire surface of a component (eg, a scaffold or a layer provided on a scaffold) is a hidden feature such as a pore. It means that it is covered with a layer including the inner surface. This can usually be accomplished using ALD now, but other processes for forming a material layer on the surface of the component also achieve the desired surface coating without departing from the scope of the present invention. Available for.

  The concepts presented herein include a variety of other than those listed above, including low capacitance capacitors, resistors, converters, transformers, diodes, transistors, and conductors, to name a few. Those skilled in the art will appreciate that the present invention is applicable for use with other microelectronic components and electronic components. It should also be understood that the invention includes a variety of different versions or embodiments, and that this “summary of the invention” is not intended to be limiting or comprehensive. That is, this “Summary of the Invention” provides a general description of one embodiment, but may also include a more specific description of some other embodiment. For example, the concepts addressed herein are applicable to both microelectronic and electronic components and methods of manufacturing or configuring subcomponents, as well as both components and subcomponents manufactured by these methods. Moreover, the use of terminology components and / or subordinate components is not intended to be limiting in any respect, and the manufacturing methods and devices disclosed in the various embodiments herein are printed circuit boards ( It should be clearly understood that a complete stand alone device that does not depend on other devices, such as "PCB") or integrated circuit ("IC") components may be included.

  Accordingly, various embodiments of the invention are illustrated in the detailed description of the invention as illustrated in the accompanying drawings and as provided herein and as embodied by the claims. . However, this Summary of the Invention does not include all of the aspects and embodiments of the present invention, and the present invention as disclosed herein includes obvious improvements and modifications thereto. Should be understood by those skilled in the art.

  Additional advantages of the present invention will become readily apparent from the following discussion, particularly when taken in conjunction with the accompanying drawings.

1 is a cross-sectional view of a sintered capacitor manufactured according to an embodiment of the present invention. FIG. 2 is a partial cross-sectional view of the sintered capacitor shown in FIG. 1. FIG. 3 is another partial cross-sectional view of the sintered capacitor shown in FIG. 1. FIG. 3 is still another partial cross-sectional view of the sintered capacitor shown in FIG. 1. FIG. 3 is still another partial cross-sectional view of the sintered capacitor shown in FIG. 1. FIG. 3 is still another partial cross-sectional view of the sintered capacitor shown in FIG. 1. FIG. 3 is still another partial cross-sectional view of the sintered capacitor shown in FIG. 1. FIG. 3 is still another partial cross-sectional view of the sintered capacitor shown in FIG. 1. 1 is a cross-sectional view of a nanoporous capacitor according to at least one embodiment of the invention. 1 is a perspective view of a scaffold used to construct a nanoporous capacitor according to at least one embodiment of the invention. FIG. 1 is a partial cross-sectional view of an electrochemical capacitor or battery according to at least one embodiment of the invention. FIG. FIG. 10 is a partial cross-sectional view of the capacitor shown in FIG. 9. FIG. 10 is another partial cross-sectional view of the capacitor shown in FIG. 9. FIG. 10 is yet another partial cross-sectional view of the capacitor shown in FIG. 9. FIG. 10 is yet another partial cross-sectional view of the capacitor shown in FIG. 9. FIG. 10 is yet another partial cross-sectional view of the capacitor shown in FIG. 9. FIG. 10 is yet another partial cross-sectional view of the capacitor shown in FIG. 9. 2 is a cross-sectional view of a nanoporous capacitor constructed on a carrier according to at least one embodiment of the invention. FIG. 1 is a cross-sectional view of an anodized nanopore capacitor comprising a nitride conductor and a plug according to at least one embodiment of the invention. 1 is a cross-sectional view of a sintered capacitor comprising a nitride conductor and a plug according to at least one embodiment of the invention.

  The drawings are not necessarily to scale, and in some instances may be exaggerated to emphasize certain parts of the invention.

  As discussed above, ALD is a manufacturing technique that allows one or more atomic or molecular layers of material to be deposited on a surface, but is not limited to, and cannot be achieved with previous techniques. It has several advantages over other manufacturing methods, including providing a consistent and reliable uniform coating thickness on exposed and hidden surfaces. A typical ALD process includes multiple cycles, and can be summarized as each cycle includes two precursor stages and two purge stages. A description of the ALD process is given in the “Background” section above.

  An ALD process for the deposition of Al2O3 will now be described by way of example but not limitation. Initially, the reaction chamber in which ALD is performed is evacuated. In the first precursor stage, the selected first precursor is introduced into the reaction chamber for the purpose of reacting with the surface. For example, trimethylaluminum (TMA) gas can be used as the first precursor to react with all surfaces in the reaction chamber. This includes the chamber itself and the surface of any one or more parts installed in the chamber. The precursor phase is continued until all surfaces are passivated. Aluminum atoms are deposited and attached to the surface, and methyl groups are attached to the Al. Longer times are needed when it is difficult to reach some surfaces, such as the inside surfaces of holes, pores, cracks and the like. Following reaction with the surface of the first precursor, a first purge step is applied by evacuating the chamber to remove any excess precursor or undesired by-products from the chamber. The An inert gas may be introduced into the chamber to better purge the precursor by essentially “flushing” the precursor.

  In the second precursor stage, the selected second precursor is introduced into the reaction chamber. Continuing the above example, water vapor can be introduced into the chamber to cause a reaction between the water vapor and unbound methyl groups present on the surface of the material. This reaction forms an aluminum-oxygen chemical bond and further forms a new surface with exposed hydroxyl groups for subsequent TMA precursor steps. After the second precursor element is introduced and the surface is passivated again, a second purge stage is applied, similar to the first purge stage, and excess precursor is drained from the reaction chamber. . Completion of the two precursor stages and the two purge stages is called one cycle. The end result of an ALD cycle using a precursor as described above results in a monomolecular layer of Al2O3 that is deposited on all surfaces open to the reaction chamber volume.

  The ALD process may include several thousand cycles, sometimes on the order of thousands, to form the desired thickness. Since each layer is deposited conformally and uniformly on the material surface and each preceding layer, the desired thickness can be accurately and consistently controlled by the number of cycles. The ALD process can be monitored and controlled by a number of well known control logic hierarchies, such as PC based, PLC (programmable logic controller) based, etc., or by other control systems.

  It is well known that the ALD process achieves very deep penetration into the pores. However, because of the very deep penetration, each stage in the cycle can be extended to account for the time for the precursor or purge gas to penetrate the pore depth. The vacuum pump connected to the chamber can be valved (disengaged) from the chamber for an extended period of time in each stage of the cycle.

  With current ALD technology, a high quality process for deposition can be achieved. By way of example and not limitation, the deposition materials are Al2O3, ZrO2, HfO2, SiO2, SrTiO3, BaTiO3, Ta2O5, TiO2, HfSiO4, La2O3, Y2O3, TiN, TaN, WN, Cu, W, TiSi2, PtSi, CoSi2, NiSi , WSi2, Si3N4 and others. It is now well known that dozens if not hundreds of materials are deposited by ALD. Materials that are well known to be deposited by ALD include dielectrics, conductors, anodes, cathodes, solid electrolytes, and others. Each molecular layer is deposited in one cycle of the process that takes about 0.5 to 5 seconds, depending on the specifications of the ALD tool.

  By way of example but not limitation, a dielectric layer made of Al2O3 will be discussed. The monomolecular layer of Al2O3 has a thickness of about 0.085 nm (0.85 cm). Other types of dielectric materials that can be used for the dielectric layer include Nb2O5, ZrO2, HfO2, SiO2, SrTiO3, BaTiO3, Ta2O5, TiO2, HfSiO4, La2O3, Y2O3, Si3N4 and other non-conductive elements or materials. Included but not limited. Although certain examples of dielectric layers will be described herein as including Al 2 O 3, the present invention is not so limited to this type of dielectric, and any other known type of dielectric One skilled in the art will appreciate that body materials can be used in place of or as a supplement to Al2O3.

  For example, assume that the dielectric layer of Al2O3 needs to have a thickness of 10 nm. To reach this thickness, 120 layers need to be deposited. Using commonly available process tools, the ALD process will take approximately 60 to 600 seconds.

ALD deposited Al 2 O 3 has a relative dielectric constant εr of about 8. The calculation of the 1 cm 2 capacitance of a parallel plate capacitor made of a 10 nm thick layer of Al 2 O 3 between two metal electrodes is as follows.
C = ε0 × εr × A / dε0 = 1 / (36 × π × 109)
Here, εr is the relative dielectric constant of the dielectric material, A is the area in m2, and d is the insulator thickness in meters. C is in Farad units C = (1 / (36 × π × 109)) × 8 × 1 × 10 −4 / 10 × 10 −9 = 7 × 10 −7 = 0.7 μF
It becomes.
Therefore, a capacity of 0.7 μF / cm 2 can be achieved.

The breakdown voltage of Al2O3 is 8 to 10 MV / cm. If 8 × 108V / m is adopted,
V = 10 × 10−9 × 8 × 108 = 8V
Using a voltage level half that of breakdown, a practical operating voltage of 4V is therefore reasonable.

  As an example of an application that requires a higher voltage, a 100 volt capacitor with 0.028 μF / cm 2 could be deposited with 3000 layers of Al 2 O 3. As will be appreciated by those skilled in the art, the material and number of layers can be varied to achieve a wide range of capacitances and voltages for such capacitors.

  There is considerable research on materials suitable for the construction of battery parts. There are several candidate materials for the anode layer configuration, including but not limited to Li4Ti5O12, Ge (Li4.4Ge), Si (Li4.4Ge), lithium titanate, or lithium vanadium oxide. The cathode layer is, by way of example and not limitation, LiFePO4, LiCoO2, LiMn2O4, LiNiO2, LiMPO4, where M represents a metal such as Fe, Co, Mn, Ti, etc., and LiFe0.95V0.05PO4 or A2FePO4F where A = It can be composed of Na, Li. The solid electrolyte layer is by way of example and not limitation, and to name a few, lithium phosphate oxynitride (Lipon), lithium lanthanum titanate (LLT), Na +, K +, Li +, Ag +, H +, Pb2 +, It can be composed of beta alumina, non-stoichiometric sodium aluminate, yttria stabilized zirconia (YSZ) or (Li, La) xTiyOz that forms a complex with a mobile ion such as Sr2 + or Ba2 +.

  In the following, various embodiments of the present invention will be described with reference to the drawings (FIGS. 1-20) in detail.

  According to an embodiment of the present invention, a method of manufacturing a sintered capacitor with a sintered capacitor and ALD is disclosed. A sintered capacitor manufactured by ALD according to one embodiment is shown in cross-section in FIG. It is important to note that the overall structure is on the order of millimeters, but since the spherical sintered particles are on the order of micrometers or nanometers, the drawing of FIG. 1 is not to scale. The sintered capacitor 100 is composed of a sintered material 104. In a preferred embodiment, the sintered material 104 also serves as one of the electrodes of the sintered capacitor 100 and is preferably made of a conductive metal. The sintered material has a fill factor of less than 100% and includes material particles and pores that are fused together by the sintering process, wherein the at least one pore extends the scaffold from the first side to the second side. To cross. A particle diameter between 0.1 μm and 10 μm is common when sintering metals, however, for calculation purposes, it is assumed to be a diameter of 1 μm by way of example and not limitation. The entire surface of the sintered material 104, including the hidden surfaces within the pores of the sintered material 104, is coated with a dielectric material 112 that may be deposited by ALD according to the method described above. The empty supplemental space left by the sintered material 104 and the dielectric material 112 is completely or partially filled with an electrode material 118 made of a conductive material. The electrode material 118 can be formed by an ALD process or according to an alternative embodiment by other processes such as wetting with molten metal or by a combination of the two processes. In a preferred embodiment, the sintered material 104 and electrode material 118 are connected to terminals 128, 144 by fillers 124, 140. In an alternative embodiment, sintered material 104 and electrode material 118 are connected to terminals 128, 144 by solders 124, 140. Insulator 132 is preferably installed to minimize the possibility of a short circuit at the outer surface. Insulator 132 is preferably made of glass or plastic material.

  In another embodiment of the present invention, the dielectric layer 112 of the previous embodiment is replaced with an anode, solid electrolyte and cathode layer made of the materials described above to make a battery or electrochemical capacitor. It is done. In an alternative embodiment, the electrode material 118 is omitted if the anode or cathode are both distant from the sintered material 104 but can carry current.

  The detailed configuration of the sintered capacitor will be better understood from the description of the embodiment of the method of manufacturing the sintered capacitor of the present invention. The configuration process is described in connection with FIGS. Referring now to FIG. 2, the sintered material 104 is shown in cross-sectional view as a sintered powder. The construction of sintered capacitor 100 begins with making sintered material 104 to form an electrode by sintering metal powder. Preferably, one or more conductive metals such as copper, brass, silver, nickel, stainless steel, etc. are used. In an alternative embodiment, metal composites such as brass and / or metal particles coated with the same or another metal are used. In another alternative embodiment, a non-metal such as a ceramic can be used if it is coated with the metal before or after sintering. During the well-known technique of sintering, the metal powder is pressed and heated to a temperature below the melting point of the material, causing local coalescence of the particles. In FIG. 2, spherical particles are illustrated, but other shapes are possible. The particles can be solid as shown in FIG. 2, or can be porous depending on the materials and techniques used. The particles can have a very uniform size or various sizes. The sintered body may have any shape or size, but cubes, right prisms or cylinders with a size of 1 mm to 10 mm are more common in production. A fill factor of 50% will be used herein by way of example and not limitation, but other fill factors may be used according to well-known sintering processes. The volume of the sintered material is porous and the at least one pore traverses the scaffold from the first side to the second side. By way of example and not limitation, if 1 micron particles are used, a 2 × 2 × 2 mm 3 sized cube will have about 4 × 10 9 particles at a 50% fill rate, and about 24,000 mm 2 Will have a total surface area. Since the actual numbers depend on particle shape, size change, etc., these are very rough estimates. For other situations, the numbers may vary according to the material structure. The sintering process results in forming an electrode composed of the sintered material 104.

  According to yet another alternative embodiment, any porous material made by various techniques can be used for the first electrode. Some porous materials have a very large surface area that is useful for making capacitors with large capacitances. If not conductive, the material may be coated with at least one conductive layer.

  According to yet another alternative embodiment, the sintered material is hardly oxidized, i.e. there is no dielectric layer covering the sintered material, if any, it is very thin and is deposited in the next step. Thinner than the dielectric layer.

  Referring now to FIG. 3, the bottom terminal 128 is preferably formed of a convenient or common conductive metal and brazed to the sintered material 104 using a filler 124. The surface of the sintered material 104 is cleaned by etching or other techniques to allow for good wetting of the solder or filler material and to remove any oxide layer in preparation for the next deposition step. Also good. The brazing process may be performed in the same chamber used for the next step of manufacture by appropriately raising the temperature above the melting point of the filler.

  In mass production, the bottom terminal 128 can be formed from a piece of sheet metal on which thousands of cubes, right prisms or cylinders of sintered material 104 are brazed. A cross-sectional view of just one cube or cylinder is shown in FIG. 3 for clarity. By way of example and not limitation, typical dimensions include a bottom terminal of about 0.5 mm thickness, 400 × 400 mm 2 width and length on which 10,000 2 × 2 × 2 mm 3 cubes are placed. , And brazed at a pitch of about 4 mm. Apart from brazing with filler 124, the sintered material 104 and the bottom terminal, such as soldering, another step of sintering, or sintering the sintered material 104 in direct contact with the bottom terminal 128, etc. Other forms of connection between 128 are possible.

  Referring now in detail to FIG. 4, a dielectric material layer 112 formed on the sintered material 104 is shown in cross-sectional view. In this step, ALD can be used to form a dielectric material layer 112 that surrounds an electrode formed from the sintered material 104. ALD is particularly useful in this step because it allows the deposition of a very closely matched layer of material into a very deep cavity. The process is self-terminating, as explained above, to create a monolayer with each cycle of the process. According to a preferred embodiment, the dielectric material layer 112 should have a high dielectric constant and high dielectric strength. A well-known material for such ALD applications is Al 2 O 3 used as an example above and below. In alternative embodiments, by way of example and not limitation, other dielectrics such as Nb2O5, ZrO2, HfO2, SiO2, SrTiO3, BaTiO3, Ta2O5, TiO2, HfSiO4, La2O3, Y2O3, or Si3N4 can be used.

Using Al2O3 as an example, this material has a dielectric constant of about 8 and a breakdown voltage between 8-10 MV / cm. As an example, but not as a limitation, assume that the goal is to produce a capacitor with an operating voltage of 10V, and that it is desired to have a working voltage of about 4 MV / cm or 4 × 10 8 V / m. For a 10 volt capacitor, the dielectric thickness is calculated as follows.
T = 10/4 × 108 = 2.5 × 10 −8 m or 25 nm

  Each molecular layer of Al2O3 has a thickness of about 0.085 nm. Therefore, about 300 layers are required for the dielectric layer 112. For different operating voltages, the thickness varies almost linearly.

  Referring now to FIG. 5, the next step is to add an insulator 132 to the side of the sintered material 104 covering the dielectric material layer 112. The reason for the insulator 132 is that it is not desirable to create the periphery of the part where the two electrodes (sintered material 104 and electrode material 118) are separated by a few nanometers (electrode material 118 is related to FIG. 6). And will be explained in detail later). According to a preferred embodiment, the insulator 132 is composed of a thermoset or thermoplastic with a high melting temperature. Alternatively, glass of various types of glass materials can be used to make the insulator 132. The coefficient of thermal expansion of the glass insulator 132 should be matched to the composite coefficient of the sintered material 104 and the electrode material 118 to allow extreme working temperatures without damaging the glass. Insulator 132 may be structured as a powder, paste, or preformed material to fill between cubes, right prisms or cylinders of individual capacitor units and then solidified or reflowed. The insulator 132 must be sufficiently viscous so that it does not invade most of the volume between the sintered particles.

  In another embodiment of the invention, the insulator 132 is placed before the dielectric 112 is formed. This variation will not change the performance of the capacitor 100 or similarly configured electrical components.

  Referring now to FIG. 6, a cross-sectional view of the sintered capacitor assembly is shown including the second electrode 118. In this step, ALD deposition of electrode material 118 is performed. Metal ALD may require a significant number of layers (up to thousands) to fill all the spaces formed between the sintered material 104 particles. ALD of metal or conductive material is preferred, but other techniques may be used to complete this step. Molten metal under vacuum conditions can be used to make electrode material 118 in a process much like soldering. A combination of first coating the metal that adheres well to the material of the dielectric layer 112 by ALD and then allowing another metal to melt can also be used. In such cases, the ALD deposition layer helps the molten metal wet the surface and infiltrate.

  In an alternative embodiment, a space may be left unfilled and closed in subsequent steps. The electrode material 118 is preferably deposited at a temperature that does not melt the insulator 132. According to one alternative embodiment, the electrode material 118 can be used as the top contact, or another material layer may be used as the top contact, as shown below.

  Reference is now made to FIG. The next step includes installing the upper terminal 144 at a desired position. As seen in FIG. 7, the upper terminal 144 is preferably brazed to the electrode material 118 using a filler 140. The top terminal 144 will preferably have the same dimensions as the bottom terminal 128 and will be brazed to all capacitors 100 in a single step. Brazing can be performed under vacuum to keep any unfilled volume of capacitor 100 evacuated and to seal all such unfilled volumes. Alternatively, brazing can be performed in a controlled environment to control what is left in the unfilled volume. After this step, the individual sintered capacitors 100 will be formed by cutting the structure in two directions in the middle of the insulator, resulting in the capacitor shown in FIG.

  A solder barrier 130 can be applied to the top and bottom terminals 144, 128, as shown in FIG. 1, which can be coated with a solder material to prepare for assembly. In an alternative embodiment, laser marking can be applied. The manufacturing processes described in the various embodiments above result in a final part as shown in FIG. The entire unit may be installed in a tape package for automatic assembly.

The capacitance of the parallel plate capacitor is calculated as follows.
C = ε0 × εr × A / d where ε0 = 1 / (36 × π × 109)
Here, εr is the relative dielectric constant of the dielectric material, A is the area in m2, and d is the insulator thickness in meters. C is in units of farads.

For the example capacitor described above,
A = 24,000mm2 or 24x10-3m2
D = 25nm or 25 × 10-9m
Εr = 8 for ALD deposited Al 2 O 3
C = ε0 × 8 × 24 × 10−3 / 25 × 10−9 = 68 μF

The completed sintered capacitor 100 of the example will have dimensions of about 3 × 3 × 3 = 27 mm 3. Specific capacitance is
68 × 10/27 = 25 V μF / mm 3
It becomes.

  A comparison of a typical tantalum electrolytic capacitor of 7 V μF / mm 3 and a typical aluminum electrolytic capacitor of 0.7 V μF / mm 3 suggests a significant improvement over current technology capacitors and manufacturing methods. Due to the construction of sintered capacitors with a high quality dielectric material, compared to electrolytic capacitors where the dielectric is made of electrically made oxide with many defects, sintered capacitors are It is expected to completely replace electrolytic capacitors in the market. A higher specific capacity will only increase the force to replace. The specific capacitances discussed above are merely examples, and different sizes and shapes of powders, different sintering processes used to make sintered materials, and different dielectric materials can produce specific capacitances. Will change. For example, the use of Ta2O5 as the dielectric will greatly increase the specific capacitance.

  In another embodiment of the invention, a battery is constructed. The dielectric layers of the previous embodiment will be replaced by the deposition of the anode layer, solid electrolyte layer, and cathode layer, all deposited in this order or in reverse order by the ALD process. There are several candidate materials for the anode layer configuration, including but not limited to Li4Ti5O12, Ge (Li4.4Ge), Si (Li4.4Ge), lithium titanate or lithium vanadium oxide. The cathode layer is, by way of example and not limitation, LiFePO4, LiCoO2, LiMn2O4, LiNiO2, LiMPO4, where M represents a metal such as Fe, Co, Mn, Ti, etc., and LiFe0.95V0.05PO4 or A2FePO4F where A = It can be composed of Na, Li. The solid electrolyte layer is by way of example and not limitation, and to name a few, lithium phosphate oxynitride (Lipon), lithium lanthanum titanate (LLT), Na +, K +, Li +, Ag +, H +, Pb2 +, It can be composed of beta alumina, non-stoichiometric sodium aluminate, yttria stabilized zirconia (YSZ) or (Li, La) xTiyOz that forms a complex with a mobile ion such as Sr2 + or Ba2 +.

  In this embodiment, the insulator is attached before or after the step of depositing the solid electrolyte to macroscopically separate the anode from the cathode at the terminal.

  In another embodiment of the present invention, the battery attaches electrode material 118 with the cathode or anode neither in contact with sintered material 104 but relying on carrying current to the second terminal. Is omitted.

  The construction of the sintered material comprising the ALD deposited anode, cathode and solid electrolyte will give a more durable structure than a conventional battery with a CVD coated carbon structure. The ability of the ALD process to deposit layers that are defect free and pinhole free is important for solid electrolyte deposition to prevent internal shorts between the anode and cathode. In addition, due to the very short ion transport distance, the battery internal resistance will be low and the battery will have a fast charge / discharge time.

  In another embodiment of the invention, an electrochemical capacitor is constructed. Similar to the previous embodiment, there is an anode layer, a solid electrolyte layer and a cathode layer, all deposited by an ALD process. By way of example but not limitation, there are several candidate materials for anode, cathode and solid electrolyte layer configurations that are similar to the materials described above for batteries.

  With reference now to FIGS. 9-17, an exemplary nanoporous capacitor 200 will be described in accordance with an embodiment of the present invention. In particular, as can be seen in FIG. 10, the capacitor 200 includes a scaffold 204 made of nanoporous Al 2 O 3 or a similar type of material. The scaffold 204 includes pores 206 having a diameter on the order of nanometers, and at least one pore traverses the scaffold from a first surface to a second surface.

  Accordingly, FIG. 9 only depicts four pores 206 in the cross section of the scaffold 204, while FIG. 10 only depicts a relatively small number of pores 206, while the scaffold 204 of the capacitor 200. It will be appreciated by those skilled in the art that the depiction of and other parts at a particular scale is not a quick and easy understanding of the present invention. In particular, the non-scaled figures are provided for clarity and to facilitate an understanding of the present invention, where thousands or millions of pores 206 are a single cross-sectional view of capacitor 200. Those skilled in the art will appreciate that they may be present. The overall assembly size is approximately a few hundred micrometers to a few millimeters on the side, and the pores 206 are tens to hundreds of nanometers in diameter. Further, the pores 206 may include lengths ranging from a few micrometers to a few millimeters.

By way of example and not limitation, a calculation of the number of pores in a 2 × 2 × 2 mm 3 scaffold 204 with an average pore diameter 206 of 100 nm is performed. The cross-sectional area of the pore 206 is
a = π × 2/4 = 3.14 × (100 × 10 −9) 2/4 = 7.85 × 10 −15 m 2.

Assume that the total cross sectional area of the pore 206 covers half of the total available area of the face of the scaffold 204. The number of pores 206 is approximately
N = 0.5 × (2 × 10−3) 2 / 7.85 × 10−15 = 254 × 106
be equivalent to.

  Accordingly, it is understood that approximately 16,000 pores 206 will be seen in the cross section of the scaffold 204.

In one embodiment of the present invention, as seen in FIGS. 9 and 10, the nanopore capacitor 200 comprises:
A nanopore scaffold 204 having a plurality of pores 206, wherein the at least one pore traverses the scaffold from a first surface to a second surface;
A conductor 208 that is conformal to the scaffold 204 and substantially all exposed surfaces of the scaffold 204 and substantially all inner surfaces of the pores, thereby serving as the first electrode of the capacitor;
A dielectric 212 that is conformal to the conductor 208;
A plug 216 that is conformal to the dielectric 212 and serves as the second electrode of the capacitor;
A bottom terminal 228 attached to the conductor 208 using filler or solder 224 and serving as a first contact area to connect the capacitor to other electronic components, wires, PCBs and the like;
An upper terminal 244 attached to the plug 216 using filler or solder 240 and serving as a second contact area to connect the capacitor to other electronic components, wires, PCBs and the like;
It consists of two terminals of the capacitor 200 and an insulator 232 disposed on the outer periphery of the capacitor 200 to physically separate substantially all of the conductive material connected to them.

  In another embodiment, electrochemical capacitors and batteries can be constructed by replacing dielectric 212 with cathode, solid electrolyte and anode layers. Some of the pores in this embodiment are shown in FIG. 11 and are greatly enlarged and not to scale. The pores are shown inside the scaffold 204. Within the pores are concentric layers of conductor 208, anode 272, solid electrolyte 274, cathode 276 and plug 216. For similar performance, the positions of the anode layer 272 and the cathode layer 276 may be reversed. The ion transport distance 278 is a distance that the ions need to move during charging / discharging. By way of example but not limitation, anode, cathode, and solid electrolyte materials can be as discussed above, and the ion transport distance 278 is approximately tens of nanometers, resulting in low resistance and fast Causes charging and discharging.

  Although FIG. 11 generally depicts a five-layer configuration within the pores of scaffold 204, those skilled in the art will appreciate that a three-layer configuration may also be utilized without departing from the scope of the present invention. Let's be done. In particular, the cathode, electrolyte, and anode layers may be provided with substantially all of the pores if the conductivity of the cathode and anode layers is sufficient to support the desired operation of the battery.

  Another embodiment of the present invention is a method of manufacturing a nanopore capacitor 200. The description of the method will help to understand the structure of the nanopore capacitor 200. A method for constructing the nanopore capacitor 200 will be described with reference to FIGS. 9, 10 and 12-17. Similar to FIGS. 1-11, FIGS. 12-17 are not necessarily drawn to scale.

  In some embodiments, the scaffold 204 is made from metallic aluminum by passing an electric current through the aluminum using an acidic electrolyte, resulting in a scaffold 204 made of Al 2 O 3 (sapphire). The construction of scaffold 204 is described in U.S. Pat. Nos. 3,574,681, 3,850,762, 4,687,551, and 5,112, which are all incorporated herein by reference in their entirety. 449 is described in further detail. In addition, Whatman Ltd. The product manufactured by and marketed as Anopore® is provided as a particle filter. See http://www.whatman.com/PRODAnoporeInorganicMembranes.aspx and http://www.2spi.com/catalog/spec_prep/filter2.shtml, which are incorporated herein by reference in their entirety. In order to be useful as a particle filter in a gas or liquid stream, the pores need to extend from the surface where the flow enters the filter to the surface where the flow exits the filter. The size of the pores 206 can be controlled by process parameters, ie, the type of electrolyte, the amount of current, and the like. Standard diameter pores are commercially available in sizes of 20 nm, 100 nm, and 200 nm. Those skilled in the art will appreciate that the size of the pores 206 used in the capacitors described herein may vary according to component design and customer preferences. Those skilled in the art will also appreciate that similar scaffolds can be made by different techniques such as directional etching of crystals through a mask and other techniques.

  Incomparably and advantageously, a very tight distribution of pore 206 sizes within the scaffold 204 can be achieved utilizing well-known processing techniques. The pores 206 are continuous and have an overall uniform diameter from the top surface of the scaffold 204 to the bottom surface of the scaffold 204. In general, there are no interconnections, branches or intersections between the pores 206, however, any interconnections, branches or intersections of the pores are, according to any of the embodiments herein, for manufacturing. Will not cause any difficulty or difference in component performance. Moreover, the materials used to construct the scaffold 204 are inert and can withstand extreme environmental conditions such as high temperatures, corrosive liquids, and others.

  Referring now to FIG. 12, the scaffold 204 of the nanoporous capacitor 200 is covered by the first conductor 208 using an ALD process that includes multiple cycles that result in multiple layers of deposition of the first conductor 208. In some embodiments, the first conductor 208 comprises a metal or semiconductor material. The first conductor 208 is provided to serve as the first electrode of the capacitor 200 and may have a thickness ranging from a few nanometers to tens of nanometers.

  As seen in FIG. 13, once the first conductor 208 is satisfactorily deposited on the scaffold 204, the scaffold 204 comprising the first conductor 208 is brazed to the base terminal 228 using a filler 224. It may be soldered or sintered. Base terminal 228 is made of metal and is used to make an electrical connection out of the capacitor to an electrical circuit external to capacitor 200. A filler 224 may also be provided to seal the pores 206 of the scaffold 204 on the bottom side of the scaffold 204 and to facilitate electrical contact between the first conductor 208 and the base terminal 228. Good. The base terminal 228 may have a thickness ranging from, but not limited to, a few hundred microns to over 1 millimeter.

  Referring now to FIG. 14, a layer of dielectric 212 is then deposited on the entire structure (scaffold 204, first conductor 208, filler 224 and base terminal 228) using an ALD process. The thickness of the dielectric 212 is designed for a given working voltage. ALD provides a mechanism to create a complete layer of dielectric 212 without defects, pinholes or any other point where first conductor 208 is exposed, thereby reducing the chance of a short circuit in capacitor 200 or Exclude. In some embodiments, the dielectric 212 has a thickness ranging from, but not limited to, a few nanometers to tens and even hundreds of nanometers depending on the required capacitance and operating voltage. You may have.

  As can be seen in FIG. 15, the insulator 232 is then installed on the outer peripheral surface of the scaffold 204. In other words, the insulator 232 is placed on the surface of the scaffold 204 whose surface will separate the entire pore 206 (ie, on the surface of the scaffold 204 where the pore opening 206 is not exposed). In some embodiments, the insulator 232 includes a thickness ranging from, but not limited to, a few hundred micrometers to over 1 millimeter.

  Referring now to FIG. 16, a plug 216 is deposited using ALD to substantially fill the remaining portion of the pore 206 that has not yet been filled by the first conductor 208 and dielectric 212. Plug 216 serves as the second electrode of capacitor 200 and may comprise a metal or semiconductor material. In some embodiments, the plug 216 includes a thickness ranging from about 10 nanometers to 100 nm. In some embodiments, the plug 216 does not fill the pores 206.

  As seen in FIG. 17, the upper terminal 244 is then soldered, brazed, or sintered to the top of the plug 216 using the filler 240. In some embodiments, the upper terminal 244 includes a thickness ranging from a few hundred microns to over 1 millimeter. The excess layer of plug 216 and dielectric 212 is then etched or ground away to reach the capacitor 200 depicted in FIG.

  The resulting capacitor 200 is by way of example but not limitation and may include a specific capacitance of 400 V μF / mm 3 compared to 7 V μF / mm 3 provided by conventional tantalum electrolytic capacitors. Moreover, the series resistance of capacitor 200 is approximately a few micro ohms and the series inductance is very low, thereby providing very high performance. Due to the configuration of the capacitor 200, it will have a high reliability, an extended operating temperature and a substantially longer average life than traditional electrolytic capacitors.

  In another embodiment, similar to the discussion above, the electrochemical capacitor and battery may have the step of depositing the dielectric 212 comprising the cathode 276, solid electrolyte 274 and anode 272 by ALD as depicted in FIG. Constructed by replacing several steps of deposition in that order or in reverse order. In this embodiment, the insulator 232 should be attached before or after depositing the solid electrolyte 274.

  According to yet another embodiment, a method of manufacturing an electrochemical capacitor or battery is provided as in the previous embodiment, but the step of depositing the first conductor 208 and plug 216 is omitted, The cathode and anode carry current to the terminals.

  9-17, the process for constructing the nanopore capacitor 200, electrochemical capacitor or battery will now be described in more detail. Similar to FIGS. 1-8, FIGS. 9-17 are not necessarily drawn to scale. After the scaffold 204 is provided, the manufacturing process continues with the fabrication of the capacitor 200, electrochemical capacitor or battery first electrode. In particular, the scaffold 204 is coated with a conductive material, thereby providing a first conductive layer 208. By way of example but not limitation, the materials used to construct the first conductive layer 208 are silver, copper, gold, indium, aluminum, tungsten, nickel, cobalt, iron, titanium, ruthenium, zinc, tin, It can be a pure metal such as tantalum, or a combination thereof. The first conductive layer 208 can alternatively or additionally be composed of a semiconductor material such as doped silicon, doped germanium, or the like. Alternatively or in addition, the first conductive layer 208 can include a metal nitride such as TiN, TaN, WN, a metal silicide such as TiSi2, PtSi, CoSi2, NiSi, WSi2, and the like. Alternatively or additionally, the first conductive layer 208 can comprise a compound or layered material. Alternatively or additionally, the first conductive layer 208 can include any conductive material or any conductive composite or layer of conductive material or composite. Preferably, the first conductor 208 exhibits a relatively low resistance, thereby making a suitable choice of metal or metal compound. Different types of layers of different materials can also be used to construct the first conductor 208. In some embodiments, if a non-metal is used to constitute at least some of the first layers deposited on the scaffold 204, then the last to be deposited on the scaffold as the first conductor 208 Some of the layers may include a metal, thereby facilitating sufficient adhesion in a later step and possibly a diffusion barrier.

  As mentioned above and as can be seen in FIG. 12, the first conductor 208 is preferably deposited using an ALD process. The ALD process allows atomic or molecular layers to be deposited in a very conformal manner. Each cycle of the ALD process deposits one atomic or molecular layer, and in order to deposit an N layer, it is only necessary to run the process for N cycles. Due to the high aspect ratio of the pores 206, other currently known deposition techniques are impractical because the central region of the pores 206 becomes insufficiently coated. The scaffold 204 may be placed on a surface that is treated so as not to accept the coating in the ALD process chamber; however, this is not a requirement. With limited contact area between the scaffold and the surface, the majority of the bottom of the scaffold will be almost completely covered. Due to the large aspect ratio, possibly up to approximately 100,000: 1, a long residence time is required for the precursor in the reaction chamber as well as a long purge time. Will be.

  The first conductor 208 is configured to serve as the first electrode of the capacitor 200 or as an electrochemical capacitor or battery first current carrying element that carries current from the battery electrode to the terminal. The first conductor 208 should have a reasonable thickness, possibly around 1-30 nm, depending on the maximum series resistance allowed. As a non-limiting example, an approximately 70 atomic layer of copper can be deposited using ALD, resulting in a thickness of approximately 10 nm. Note that the first conductor 208 can be omitted if the anode or cathode are both deposited first but have sufficient electrical conductivity for proper operation in the final part.

  In some embodiments, a diffusion barrier layer may be deposited on the scaffold 204 prior to the deposition of the first conductor 208 to prevent metal diffusion into the scaffold 204. Another barrier layer may be deposited after deposition of the first conductor 208 to improve adhesion to the electrical contacts made in the next step and possibly prevent diffusion into the dielectric.

  The vacuum conditions and high temperatures used in connection with the ALD process are maintained for a predetermined time prior to initiating the coating process, particularly in an attempt to remove any moisture trapped in the scaffold 204 after manufacture of the scaffold in an acid bath. Also good. In addition, active reagents may be introduced into the reaction chamber such that they are chemically attached to impurities and removed.

  The next step depicted in FIG. 13 includes attaching the base terminal 228 to the scaffold 204. This base terminal 228 will serve as the first electrical contact of the capacitor, electrochemical capacitor or battery 200 and will also facilitate the connection point for a wire or similar electrical contact. In some embodiments, the base terminals 228 will be soldered directly to the PCB pads using, for example, surface mount technology.

  The attachment of the base terminal 228 will be done in such a way as to have good electrical contact in substantially the majority of the openings in the pores 206 and to the adjacent first conductor 208. This is essential to achieve a low series resistance. The thickness of the first conductor 208 can range from a few nanometers to tens of nanometers, and the base terminal 228 is generally conformal to such a degree to the flatness of the scaffold 204. There is no need. The base terminal 228 can be sintered by heating it to a temperature that matches the desired shape, perhaps by applying force, possibly by applying force. It should be noted that the scaffold 204 includes a very hard material. In some embodiments, adhesion can be achieved by brazing, in which a thin layer of filler 224 is disposed between the base terminal 228 and the first conductor 208. The filler layer 224 should be thin so that it does not so much infiltrate into the pores 206. The filler 224 can be electroplated to the base terminal 228 to a precise thickness or can be rolled with the base terminal 228.

  Sputtering, evaporation, CVD or similar techniques can be used to cover one side of the scaffold 204 with a metal layer of material that becomes part of the filler 224. Due to the limited penetration of the CVD, vapor deposition or sputtering process, a very limited amount of filler 224 will eventually enter the pores 206. However, the pores 206 will be effectively closed on the bottom side where the filler 224 is deposited, thereby causing the base terminal 228 to be in the scaffold 204 without filling or slightly filling the pores 206 of the scaffold 204. Allows brazing or soldering.

  If the previous step resulted in an unsatisfactory thickness of the first conductor 208 at the bottom of the scaffold 204, possibly due to the large contact area with the surface on which the scaffold is placed in the process chamber, The top surface of the scaffold 204 and the first conductor 208 may be attached to the base terminal 228 (ie, the scaffold 204 is turned upside down between FIGS. 12 and 13).

  In some embodiments, ALD deposition of the first conductor 208 is utilized, and then in the same chamber, a metal CVD, vapor deposition, sputtering or the like that closes the top of the pore 206 to the top of the scaffold 204 almost or completely in the same chamber. Are used. The scaffold 204 may then be placed upside down on the base terminal 228 for soldering or brazing.

  In some embodiments, the ALD process for depositing the first conductor 208 is performed while the scaffold 204 is placed on the base terminal 228. Following the ALD process, which also possibly resulted in the coating of the base terminal 228, the temperature is raised to achieve the brazing step. In this scenario, a thin layer of conductor is deposited on top of the filler 224 that is sintered to the first conductor 208 of the scaffold 204, and the filler 224 can soften for complete area contact.

  In some embodiments, it is a well-known technique to produce nanoporous Al 2 O 3 in such a way that one side of every pore 206 ends with a conductive material on one side of the scaffold. See, for example, US Pat. No. 6,838,297, which is incorporated herein by reference in its entirety. In such embodiments, a separate and different step of attaching base terminal 228 to scaffold 204 is avoided. The step of depositing the first conductor 208 is performed with the base terminal 228 already attached.

  One large metal plate can be used as the base terminal 228 and can be used to deposit hundreds or thousands of scaffolds + conductors 204 + 208 units, and later in the production process individual units (ie individual capacitors 200, electrochemical Note that it will be separated into capacitors or battery units).

  As can be seen from FIG. 14, the next step in the manufacturing process includes depositing a dielectric 212 on the structure. Dielectric 212 is preferably deposited using an ALD process and provided to serve as a dielectric for capacitor 200. The dielectric 212 must be free of defects and pinholes to avoid internal shorts that can cause the capacitor to fail. The ALD process is unmatched enough to meet such needs.

  In some embodiments, the dielectric 212 includes a metal oxide such as Nb2O5, Ta2O5, Al2O3, ZrO2, HfO2, SiO2, TiO2, La2O3, Y2O3, HfSiO4, SrTiO3, BaTiO3, or a nitride such as Si3N4. But you can. Many other dielectric materials can be used without departing from the scope of the present invention. It may be beneficial to use a combination of materials such as an Al2O3-HfO2 stack or a mixture such as (Al2O3) x (HfO2) 1-x, HfAlO (N), HfSiO (N), HfxSi1-xO2, etc. All such deposits and many more are techniques well known in the ALD field, and there are more dielectric material studies for ALD processes.

  By way of example but not limitation, Al2O3 is a very common material deposited by ALD, and approximately 118 molecular layers of Al2O3 are required to make a 10 nm thick layer. Al 2 O 3 is relatively easy to deposit using highly volatile trimethylaluminum (“TMA”) as one of the precursors. The high volatility of TMA will help deep penetration of dielectric 212 into pores 206 in process chambers that contain thousands or millions of assemblies.

  The dielectric constant of the dielectric can be lower if the dielectric 212 is not tightly packed, which can happen if an amorphous structure is made. For example, the dielectric constant of crystalline Al 2 O 3 is between 9 and 11 depending on the crystal's optical axis direction, but between 7 and 8 for ALD deposition.

  A thin barrier layer may be deposited before and after the dielectric layer 212 is deposited to prevent diffusion of the metal into the dielectric. A common barrier for copper is TaN.

  Note that dielectric layer 212 is depicted in FIG. 14 as covering the bottom of base terminal 288. This may be prevented by providing a special blocking material at the bottom of base terminal 228 during the ADL process in which dielectric 212 is deposited. Following the ALD process, the blocking material may be removed, thereby exposing the terminals 228. Alternatively, the dielectric 212 may be deposited on the bottom of the base terminal 228 and later removed by etching or grinding.

  The next step in the manufacturing process is depicted in FIG. 15, where an insulator 232 is placed around the structure. The insulator 232 may be made of glass or plastic. Insulator 232 is useful to separate the two electrodes of capacitor 200 and to allow handling of the unit by soldering to a PCB substrate or the like. This is difficult if the two electrodes are not a dielectric 232 because they are separated by a few nanometers or tens of nanometers.

  Insulator 232 should have good adhesion to dielectric 212. Alternatively, a thin layer of material with good adhesion to insulator 232 is deposited after dielectric 212 is deposited. In some embodiments, the insulator 232 is attached to the structure on four sides of the scaffold 204 if the scaffold is a cube or right prism as depicted in FIG. 10, or if the scaffold is a cylinder ( (Not shown), it is attached to the outer periphery and not attached to the top and bottom surfaces of the scaffold 204 where the pores 206 end. It is possible that the glass is melted and reflowed around the unit. Plastics such as epoxy resins may be applied. The insulator 232 should be low outgassing so as not to damage the next ALD step. If glass is used, the coefficient of thermal expansion can be selected to match the composite coefficient of other parts of the structure.

  The order of depositing the dielectric 212 and placing the insulator 232 can be reversed with no significant difference in the final product.

  Following the addition of insulator 232, the manufacturing process continues as can be seen in FIG. In particular, the second electrode of the capacitor 200 or the second electrical contact of the electrochemical capacitor or battery is configured as a plug 216. Plug 216 is constructed by utilizing an ALD process in which a conductive material similar or identical to first conductor 208 is added to the structure. In some embodiments, the material used for the plug 216 is different from the material used for the first conductor 208 (eg, one is a metal and the other is a different metal, or one Is a metal material, but the other is a semiconductor material or a metal nitride, etc.).

  In some embodiments, the plug 216 substantially fills the voids of the pores 206 that have not yet been filled with other materials. The number of ALD molecules or atomic layers added to form plug 216 can be such that even the largest pores 206 are filled.

  In some embodiments, the ALD layer of plug 216 will be designed not to fill all of the pores 206, in which case subsequent CVD, evaporation, sputtering or similar deposition processes may be opened. The closed pores 206 can be closed and sealed. In such cases, some confined voids may be present in one or more of the pores 206, but such voids may be with low pressure gas from a CVD, vapor deposition or sputtering process. If filled and sealed from the environment, then the operation of the capacitor, electrochemical capacitor or battery should not be compromised.

  In some embodiments, some pores 206 are left exposed and processed in subsequent manufacturing steps.

  In some embodiments, a thin barrier layer may be deposited after the plug 216 is deposited to prepare the surface for the next step.

  As with the dielectric 212, the plug 216 may be provided to cover the structure as a whole.

  The upper terminal 244 is then provided in the next manufacturing step depicted in FIG. As can be seen in FIG. 17, the top terminal 244 is depicted as being brazed to the plug 216 using a metal filler 240. However, soldering may be used. In both options, the soldering or brazing can be performed in a vacuum condition or controlled environment, so that any voids or exposure of the pores 206 remain filled or sealed, either vacuum or control material Containing. Alternatively, the top terminal 244 can be fabricated directly on the plug 216 by electroless plating, electroplating or any other process that can produce a thick layer of metal of the desired composition.

  If the configuration is made up of many units that share a large bottom terminal 228 and top terminal 244, cutting the structure in two orthogonal directions along the center of the insulator 232 will result in individual capacitors, batteries Or used to separate electrochemical capacitors.

  The final manufacturing step is to remove unwanted plugs 216 and dielectric 212 by etching or grinding. Some thickness of insulator 232 and terminals 228, 244 may be removed as well. After the unwanted plug 216 and dielectric 212 are removed, the completed capacitor 200 depicted in FIG. 9 is achieved. In some embodiments, a solder barrier similar to the solder barrier 130 in FIG. 1 may be attached if desired.

For performance calculations, by way of example but not limitation, the capacitor is made from a 1 × 1 × 1 mm 3 nanoporous Al 2 O 3 scaffold 204 with an average pore 206 diameter of 70 nm, and the conductor layer 208 is 10 nm thick. Yes, the dielectric layer 212 is assumed to be 10 nm thick and the plug 216 diameter is nominally 30 nm. The cross-sectional area of the pore 206 is then
a = π × D2 / 4 = 3.14 × (70 × 10 −9) 2/4 = 3.85 × 10 −15 m 2
It is.

Assume that the cross-sectional area of the pore 206 covers half of the total available area of the scaffold 204. The number of pores 206 is approximately
N = 0.5 × (10−3) 2 / 3.85 × 10−15 = 130 × 106
be equivalent to.

The outer periphery of the dielectric 212 at the center thickness (diameter 40 nm) is
b = π × D = 3.14 × 40 × 10 −9 = 126 × 10 −9 m
It is.

The total capacitor electrode area is
A = N × b × h = 130 × 106 × 126 × 10 −9 × 10 −3 = 16.4 × 10 −3 m 2
It is.

The capacitance of the parallel plate capacitor is
C = ε0 × εr × A / d where ε0 = 1 / (36 × π × 109)
It is.

Where d is the thickness of the dielectric 212 in meters. C is in units of farads. Assume an Al 2 O 3 dielectric with εr = 7.
C = (1 / (36 × π × 109)) × 7 × 16.4 × 10 −3 / 10 × 10 −9
= 0.101 × 10 −3 F = 100 μF

A 10 nm thick Al 2 O 3 will have a breakdown voltage of 8V, and a working voltage of 4V is assumed. Therefore, the specific capacity is
100 × 4/13 = 400 V μF / mm 3
It will be.

  Those skilled in the art will appreciate that an excellent capacitor can be realized when compared to a tantalum electrolytic capacitor of 7 V μF / mm 3. The insulator and terminal will reduce the specific capacitance as calculated above by an amount depending on the dimensions of the capacitor.

Low resistance and inductance are significant problems for useful capacitors. Calculating the series resistance of the capacitor includes coupling all conductors 208 and plug 216 layers in parallel. Assuming the same example, assuming both the conductor and the plug are made of copper,
R = (1.72 × 10 −8 × L [m] / S [m2]) / N
≒ (1.72 × 10-8 × 10-3 / (π × (30 × 10-9) 2) / 4) / 130
× 106
= 18.7 × 10 −5 Ω = 187 μΩ

  Such a low resistance allows fast energy charge / discharge, again again allowing very desirable capacitor quality.

  Due to the linear flow of current in the capacitor, the inductance will be very low.

  In another embodiment of the present invention, the method of manufacturing the battery and electrochemical capacitor is similar to the previous embodiment with some modifications. Although the overall configuration is the same, the steps of depositing dielectric 212 are depositing a layer of anode 272, depositing a layer of solid electrolyte 274 and a layer of cathode 276, as depicted in FIG. Are all deposited, preferably by ALD techniques. The layers may be deposited in reverse order to achieve similar performance.

  Cathode 276 is, by way of example and not limitation, LiFePO4, LiCoO2, LiMn2O4, LiNiO2, LiMPO4, where M represents a metal such as Fe, Co, Mn, Ti, etc., and LiFe0.95V0.05PO4 or A2FePO4 where A = ALD is deposited from Na, Li.

  The solid electrolyte 274 is by way of example and not limitation, and a few examples include lithium phosphate oxynitride (Lipon), lithium lanthanum titanate (LLT), Na +, K +, Li +, Ag +, H +, Pb2 +, ALD deposited from beta alumina, non-stoichiometric sodium aluminate, yttria stabilized zirconia (YSZ) or (Li, La) xTiyOz that forms complexes with mobile ions such as Sr2 + or Ba2 +. The ability of the ALD process to create a defect-free and pinhole-free layer is important for solid electrolyte deposition because it prevents internal shorts between the anode and cathode.

  The anode 272 is, by way of example and not limitation, ALD deposited from Li4Ti5O12, Ge (Li4.4Ge), Si (Li4.4Ge), lithium titanate or lithium vanadium oxide.

  In order to keep the electrical separation between the cathode and anode at a macroscopic level, the insulator 232 should be attached before or after the solid electrolyte is deposited.

  Due to the structure, ions do not need to transport distances 278 longer than tens or hundreds of nanometers during charge and discharge, thereby reducing series resistance and charge and discharge time constants.

  In operation, current flows through the battery or electrochemical capacitor from external electrical wiring to terminal 228, to filler 224, to conductor 208, and from there to anode 272. From the anode 272 to the cathode 276, current will be carried by ions that penetrate the solid electrolyte 274 and travel through the ion transport distance 278. From the cathode 276, current flows to the external wiring through the plug 216, the filler 240, and the terminal 244. A somewhat different sequence is possible if the cathode 276 is deposited adjacent to the conductor 208 and the anode 272 is deposited adjacent to the plug 216. In addition, current flows in reverse during the charge / discharge cycle. The series resistance of the battery consequently consists mainly of the conductor 208, the plug 216 and the ohmic resistance of the ion transport resistance. The ion transport distance is small, on the order of tens of nanometers, resulting in a small resistance.

  In an alternative embodiment, conductor 208 and plug 216 may be omitted, relying on anode 272 and cathode 276 to conduct current along the pore length. In such embodiments, the electrical resistance of anode 272 and cathode 276 should be suitable for the final product.

  Due to the huge aspect ratio of the pores, in the above example 14,000: 1 and possibly 100,000: 1, current ALD devices and depositions in which the precursor is pulsed briefly into the process chamber This method may not be suitable. The long residence time of each precursor in the chamber to allow time for the molecules to reach the farther surface inside the pores, and most of the molecules are removed from the pores before the next precursor is in It may be desirable to have a long purge time between the precursors for. An inert gas may be used between the precursors to aid in the purge, again requiring a long residence time and long pumping. To avoid wasting excessive precursor, the reaction chamber may be disconnected from the vacuum pump for a long residence time.

  The deposition method is consequently achieved by first pumping the process chamber to the appropriate vacuum and then closing the valve between the process chamber and the vacuum pump. A chemical dose of the first precursor is then released into the process chamber. The dose should be sufficient to cover the pores 206 and all exposed surfaces of the chamber with some margin. The valve is then opened and the unusable precursor and reaction residues are pumped out. Purge gas is then flowed into the reaction chamber. During this step, the vacuum pump may be disconnected to allow longer residence time of the purge gas, but this is essential as the purge gas is cheap and may not be a problem for the environment. Absent. The process continues with the second precursor being handled in the same manner as the first precursor.

  The production process includes hundreds or thousands of molecules or atomic layers deposited by ALD technology, depending on the required parameters of the final product. Each cycle of layer deposition is longer than other ALD processes. This is not a cost issue because, due to the deep and complete penetration of the ALD process, thousands or millions of parts can share one large process chamber with a total volume that can be larger than 1 meter cubic. .

  Referring now to FIGS. 18-20, alternative capacitor, electrochemical capacitor and / or battery configurations and methods of manufacturing the foregoing will be described in accordance with at least some embodiments of the present invention. As with FIGS. 1-17, FIGS. 18-20 are not necessarily drawn to scale to facilitate a better and clearer understanding of the present disclosure.

  Referring initially to FIG. 18, an example capacitor 300 is depicted as being configured on a carrier 301. The carrier 301 is part of a semiconductor chip, chip carrier, ceramic composite, multichip module (“MCM”), PCB, and the like. The surface of the carrier 301 is made of an insulating material 332. Scaffold 304 is provided in the required dimensions. The scaffold 304 is coated with a first conductor 308 and then attached to the carrier 301, for example by brazing using a filler material 324. The first conductive region 350 may correspond to an electrical contact pad or any other point with electrical connectivity on the carrier 301.

  Although only one capacitor 300 is depicted in FIG. 18, a single carrier 301 may have one or more capacitors 300 configured thereon according to the manufacturing process described herein. Those skilled in the art will understand. In addition, the plurality of capacitors 300 can be simultaneously attached to the carrier 301.

  In an alternative embodiment, the scaffold 304 may be first attached to the carrier 301 and then the conductor 308 is deposited. If the scaffold 304 is made of a material that does not wet the filler 324 easily, the scaffold 304 may initially apply any conductive material that will wet the metal or filler 324 to its bottom surface for brazing purposes. It may be coated.

  Once the scaffold 304 is attached to the carrier 301, the fabrication of the capacitor 300 continues with the deposition of the dielectric 312. In some embodiments, the dielectric 312 is deposited over the entire carrier 301 including the scaffold 304 and areas without the scaffold 304. Where the second conductive region 352 is exposed (ie, it is not covered by the scaffold 304), the dielectric 312 is generally undesirable. Accordingly, in some embodiments, the dielectric 312 deposited on the second conductive region 352 is one that is mechanically ground, etched away, or removed by laser ablation. is there. In some embodiments, the carrier 301 with the scaffold 304 together defines a surface that is far from a plane, so utilizing a laser to remove unwanted dielectric 312 is more effective. Sometimes I understand. In some embodiments, a material that prevents the deposition of the dielectric 312 is placed in the second conductive region prior to the deposition of the dielectric 312 and removed after the dielectric 312 is deposited.

  The function of the insulator 232 (in FIGS. 9-17) may now be performed by the insulating material 332 of the carrier 301. That is, the isolation insulator is not necessarily required when the capacitor 300 is directly connected to the carrier 301. This is possible because the electrodes are not accessible and are protected in a further step.

  Once the dielectric 312 is removed from areas where it is not needed, a plug 316 is deposited. In some embodiments, the plug 316 is shaped to completely fill the pores 306. Alternatively, the final step of CVD, vapor deposition or sputtering is used to finally fill or seal the pores 306. In addition to covering the scaffold 304, the plug 316 also covers the dielectric 312 on the carrier 301 as well as the exposed second conductive region 352. Since the plug 316 operates as the second electrode of the capacitor 300, the capacitor 300 is provided from the first conductive region 350 to the second conductive region 352.

  The top material layer 354 is then deposited using CVD, sputtering, electroless deposition, electroplating, or any other mechanism known to deposit a relatively thick layer of material. This is done to ensure that the connection between the plug 316 and the second conductive region 352 is reliable and has a relatively low resistance. In some embodiments, selective deposition may be performed, for example, by electroplating, while some regions are protected with a non-conductive layer.

  In some embodiments, the scaffold 304 deposits aluminum over the carrier 301, removes aluminum from unwanted areas, and anodizes the aluminum until the pores 306 reach the conductive material 350. Can be made in situ on top. Details of this process are described in US Pat. No. 6,838,297, the entire contents of which are hereby incorporated by reference herein.

  In another embodiment, similar to the discussion above, the electrochemical capacitor and battery may perform a step of depositing dielectric 312 by cathode, 276, solid electrolyte 274 and anode 272 by ALD as depicted in FIG. Constructed by replacing several steps of deposition in that order or in reverse order.

  In another embodiment, similar to the previous embodiment, the step of depositing conductor 308 and plug 316 is omitted and the cathode and anode carry current along the length of pore 306.

  The device resulting from the above method is an on-module-type electrical element. In some embodiments, capacitors having the depicted scaffolds 304, pores 306, layers of conductors 308, dielectrics 312 and the like are made. On-module capacitors can be easily delivered by the carrier 301, and mass production of such on-module capacitors on a common carrier is easily obtained. In some embodiments, on-module electrochemical capacitors and batteries are made that include cathode and anode layers as opposed to capacitor dielectric layer 312. Multiple on-module electrochemical capacitors and batteries can be fabricated on a single carrier 301, thereby facilitating efficient fabrication of multiple electrical elements.

  Referring now to FIG. 19, another example capacitor, battery, or electrochemical capacitor 400 is depicted in accordance with an embodiment of the present invention. In particular, an anodized nanopore capacitor 400 comprising a non-metallic conductor 408 and a plug 416 is depicted. The overall dimensions of the capacitor, battery, or electrochemical capacitor 400 and its components are similar to one or both of the capacitor, battery, or electrochemical capacitors 100 and 200 and their components.

  In current ALD technology, metal deposition has been extensively studied, but has technology available to deposit metal inexpensively into deep pores with aspect ratios substantially greater than 1000: 1. Could be time consuming. The research and deposition of TiN, TaN, WN and other nitrides and metal silicides such as TiSi2, PtSi, CoSi2, NiSi, WSi2 are commonly done. Nitride has a substantially higher resistance than metal, about 10 to 1000 times higher. The metal has 1.7 to 10 μΩcm (1.7 to 10 × 10 −8 Ωm) and the as-deposited nitride has 100 to 1000 μΩcm. However, if properly designed, a nanoporous capacitor, battery, or electrochemical capacitor 400 comprising a nitride, silicide or other non-metallic conductor 408 and a plug 416 is better than existing electrolytic capacitors. Resistance performance can be achieved. In addition, capacitors constructed using at least one nitride, silicide, or other non-metallic conductor and / or plug are easier and more cost effective than comparative capacitors with different types of pure metals as conductor plugs. Can be manufactured. As an example, an ALD process for depositing nitrides, silicides, or other non-metallic materials is somewhat easier to perform at a pore depth than an ALD process for depositing pure metals. In order to be able to make electrical contacts, there will be a need for metal deposition, but only exposed surfaces, not in deep pores.

  The capacitor, battery, or electrochemical capacitor 400 of FIG. 19 is depicted as having a scaffold structure 404 in which the pores are defined. The scaffold is made of a nanoporous material as described above, with at least one pore traversing the scaffold from the first side to the second side.

  Another embodiment of the present invention, depicted in FIG. 20, contemplates the use of sintered materials for a capacitor, battery, or scaffold 504 of an electrochemical capacitor 500. In some embodiments, sintered metal may be utilized as the sintered material for scaffold 504. Sintered stainless steel and sintered brass are commercially available for use as particle filters with a pore size of about 500 nm, but can also be made to have a smaller pore size. Use as a particle filter demonstrates that there are many pores that traverse the sintered material from the first side to the second side.

  Capacitor, battery, or electrochemical capacitor 500 includes a sintered material scaffold 504 that is a macroscopic mass of material having microscopic pores therein. The pores are neither straight nor uniform and intersect and do not have a uniform diameter, as in the scaffold 404 of the capacitor, battery, or electrochemical capacitor 400, but still the capacitor, battery, or electricity. Suitable for use as a chemical capacitor. At least one pore traverses the scaffold from the first surface to the second surface.

  The dimensions of the capacitor, battery or electrochemical capacitor 400, 500 and its components are similar to the dimensions of the capacitor depicted in FIGS.

  In some embodiments, the sintered material scaffold 504 can be used as a conductor to save one step of ALD deposition. However, a good, non-oxidized surface must be maintained for the majority of the sintered material scaffold 504. By using the sintered material 504 only as a scaffold and not using its conducting ability, a capacitor, battery, or electrochemical capacitor can be manufactured with performance similar to the anodized aluminum scaffold-type capacitor 400. The only difference between capacitors 400 and 500 is that the pores are not straight and do not align, but rather are interconnected in capacitor 500 with sintered material scaffold 504.

  In the embodiment depicted in FIGS. 19 and 20, a layer of conductors 408, 508 is deposited over the entire surface of scaffolds 404, 504. Exemplary types of materials that may be used for conductors 408, 508 include, without limitation, TiN, TaN, WN, TiSi2, PtSi, CoSi2, NiSi, and WSi2. Conductors 408, 508 serve as the first electrode of the capacitor and as an electrical conductor that carries current to the capacitor, battery or electrochemical capacitor structure.

  The first side of the structure will have good adhesion and electrical contact to the conductors 408, 508, have reasonable electrical conductivity, and will easily wet the metal for further steps; Top contacts 436, 536 made by deposition of metal, several metal layers, composites or any material that is not or very shallow intrusions into the pores of scaffolds 404, 504 as discussed above. There is.

  Upper terminals 444, 544 are brazed to upper contacts 436, 536 using upper filler material 440, 540.

  Dielectric layers 412 and 512 are deposited over the entire surface of conductors 408 and 508.

  Plugs 416 and 516 are deposited on the entire surface of the dielectrics 412 and 512. In some embodiments, the material used to construct the plugs 416, 516 is similar or identical to the material used to construct the conductors 408, 508. Also, in some embodiments, the plugs 416, 516 may or may not completely fill the pores of the scaffolds 404, 504. The plug serves as an electrical conductor that carries the function and current of the second electrode of the capacitor to the capacitor, battery or electrochemical capacitor structure.

  On the second side of the scaffolds 404, 504 (opposite the top surface), bottom contact layers 420, 520 similar to or made of the same material as the top contacts 436, 536, similar to the top contacts 436, 536, Deposited on plugs 416, 516. Bottom terminals 428, 528 are brazed to bottom contact layers 420, 520 using bottom filler material 424, 524.

  Around the scaffolds 404, 504, insulators 432, 532 are macroscopic from any conductive material in electrical contact with the conductors 408, 508 from any conductive material in electrical contact with the plugs 416, 516. Provided to be separated.

  In another embodiment of the present invention, the electrochemical capacitor or battery is configured similar to the previous embodiment, but the dielectrics 412, 512 have an anode 272, a solid electrolyte as depicted in FIG. 274 and cathode 276 layers are replaced. FIG. 11 depicts a portion of the pores of the scaffold 404 or 504. The lines depicted with respect to the scaffolds 404, 504 and the various other layers around them may or may not be straight, but the thickness of such layers is uniform It should be noted.

  In another embodiment of the invention, the electrochemical capacitor or battery is configured similar to the previous embodiment, but relying on cathode 276 and anode 272 to carry current along the pore length. , Conductor 208 and plug 216 are absent.

  In the case of an electrochemical capacitor or battery, insulators 432 and 532 separate between anode 272 and cathode 276. The positions of anode 272 and cathode 276 may be reversed with similar performance.

Another embodiment of the present invention is a method of manufacturing capacitors 400, 500, which includes the following steps.
a. In one embodiment, creating scaffolds 404, 504 by anodizing aluminum to create nanoporous Al2O3. In another embodiment, by sintering powder, preferably metal powder. The conductivity of the metal powder does not significantly affect the electrical performance. The scaffold should have a plurality of pores, and at least one pore traverses the scaffold from the first side to the second side.
b. Scaffolds 404, 504 are conductive layers 408 made of TiN, TaN, WN, TiSi2, PtSi, CoSi2, NiSi, WSi2 or any other material with a fairly good conductivity, better than about 1000 μΩcm by ALD process. Coating with 508; The conductor material may be annealed after deposition to improve conductivity. The ALD process used to deposit the conductor should allow very deep penetration into pores with aspect ratios greater than 10,000: 1. A long residence time for each precursor dose is desirable to allow complete penetration, but this is not a cost issue due to the possibility of mass deposition in very large chambers. At least one end of the scaffold where the pores end at the scaffold 404 or at any end of the scaffold 504 is similarly coated.
c. Deposition step of top contact material 436, 536. This is preferably a metal that will have good wetting of other metals. It is deposited by CVD, sputtering, evaporation, or any other deposition process that can create a layer of top contacts 436, 536 on the first side of the scaffolds 404, 504 with minimal penetration into the pores. ALD can be used as well if it is specifically designed to have low penetration. Having some metal deposited on any other outer surface area is not required, but does not cause a problem. Many metals are possible including nickel, chromium, zinc, gold, tungsten, ruthenium, palladium, silver, metal composites, layered metals and others. A prerequisite is slow oxidation to minimize the need for a fairly high melting temperature to avoid melting in subsequent steps and an inert atmosphere between steps. If some or all of the pores are to be completely occluded at the first surface by the top contacts 436, 536, the requirement is acceptable. The top contacts 436, 536 may be flushed with a thin layer of noble metal to prevent oxidation until the next step.
d. Brazing upper terminals 444, 544 to upper contacts 436, 536; Filler materials 440, 540 are used as in common brazing techniques. The top contacts 436, 536 do not penetrate deeply into the pores, so if the conductors 408, 508 do not have good wetting of the fillers 440, 540, the filler material 440, 540 will enter and fill the pores. There is almost no risk of doing. In some embodiments, the upper terminals 444, 544 are a bulk metal, such as copper or a copper alloy, and the upper fillers 440, 540 are brazing fillers having a selected melting temperature. The top terminals 444, 544 may be made of several layers of metal and the outer layer is ready to be soldered to the PCB and is preferably designed to serve as a solder barrier . The top terminals 444, 544 may be made from a metal alloy that has a similar coefficient of thermal expansion as the rest of the structure to minimize stress, or it may provide thermal stress without damaging the structure. It may be flexible enough to accept. The filler thickness should be sufficient to absorb the flatness difference between the upper terminals 444, 544 and the ends of the scaffolds 404, 504. It is desirable to braze without flux to avoid the need for cleaning, so the top contacts 436, 536 and fillers 440, 540 should be substantially free of oxidation. An inert atmosphere may be used between steps to prevent oxidation. In addition, a thin layer of noble metal may cover the fillers 440, 540 prior to the brazing step.
e. Deposition steps of dielectrics 412, 512 that can be one of many available, such as Al2O3, Ta2O5, other metal oxides, Si3N4, layers of different materials or mixtures of materials as previously discussed . The very deep penetration of insulating materials, especially Al2O3, by the ALD process is a well-known technique. ALD produces a high quality deposited layer free of pinholes, defects and the like. The deposition process can be designed to create an amorphous structure rather than a crystalline structure to improve the insulation quality. A layer that is free of defects throughout the inner surface of the pore and free of pinholes is important. Again, a long residence time for each precursor dose is desirable to achieve full penetration into the full depth of the pore.
f. Installing insulators 432, 532 on all sides of scaffolds 404, 504 by reflow or casting of glass or plastic material. The glass should be made from a composition having a coefficient of thermal expansion that is quite similar to the remaining composite coefficient of the structure so that the stress across the size of the entire configuration is not too great. Plastics can receive stress even if there is a large difference in expansion coefficient. The plastic should be selected to have low outgassing properties so as not to damage subsequent steps. Without insulation, insulation becomes difficult to use by soldering the wire to the assembly or by soldering the assembly directly to the printed circuit board due to nanometer separation of the electrodes The body is very important for the usefulness of the final assembly. Note that this step f may be performed before step e without significant changes in performance. In another embodiment, a thin layer of glass and a plastic layer or other mixed configuration can be used as well. The glass layer can be approximately 1 to several tens of microns thick and can be deposited in this step f, while the hundreds of micron plastic layer is later processed in the process after the plug material has been removed from the glass surface. Will be installed. In this way, the need to install any plastic material in the ALD deposition chamber is avoided.
g. Deposition step of plugs 416, 516 by ALD. Plugs 416, 516 are made of the same conductive material as conductors 408, 508 or different materials with similar characteristics. In order to have similar conductivity as the conductors 408, 508, the plugs 416, 516 can include thicker layers due to their smaller diameter. The plugs 416, 516 preferably will completely fill the pores, but that is not a requirement. Again, as with the deposition of conductors 408, 508, the plug 416, 516 deposition process should facilitate deep penetration into the pores.
h. Depositing bottom contact material 420, 520 on the second side of the assembly; This is a metal similar to the top contacts 436, 536, and may be the same or different metal. It is deposited by ALD, CVD, sputtering, evaporation, or any other deposition process that can create a metal layer on one side of the scaffold. The bottom contacts 420, 520 may block any pore openings that were not filled by the plugs 416, 516.
i. Brazing bottom terminals 428, 528 to bottom contacts 420, 520 using bottom fillers 424, 524, sealing all pores that are not completely filled so that environmental material can enter the pores. Finally make sure to prevent. The bottom terminals 428, 528 may be the same material as the top terminals 444, 544, but the bottom fillers 424, 524 should have a lower melting temperature than the top fillers 440, 540. This step is preferably performed in a vacuum or selected atmosphere to control what is confined to any open pores that are finally plugged.
j. If steps b to i are shared among many capacitors in the array, separating the individual capacitors 400, 500. Mechanically or chemically removing all unwanted dielectric, plug and bottom contacts exposed to the surface and not desired.

  It should be noted that the top and bottom terminals may be deposited directly on the top and bottom contacts by techniques that can create a thick layer of metal, such as electrochemical or electroless deposition. Such a thick deposition technique is performed in a liquid if the top terminal is deposited in this way, so the electrolyte should be completely removed from the pores before further steps. If the bottom terminal is deposited in such a manner, the pores are completely filled by the plug or completely blocked by the bottom contact to avoid trapping any liquid in the pores. It must be done. Alternatively, if the top contacts 436, 536 and the bottom contacts 420, 520 are deposited in such a way that all the pores are sealed, then the terminals 428, 444, 528 and 544 are step j May be deposited together directly in a liquid environment.

  It should also be noted that a diffusion barrier layer may be deposited to prevent diffusion of material from layer to layer. Some diffusion may be unavoidable or even desirable, for example, between the contact layer and the filler material.

  The seed layer may be used to allow good adhesion of the contact layer material to the conductors and plugs. For example, a metal seed layer may be deposited on a conductor or plug by ALD or CVD, and contacts are then deposited on the seed layer by sputtering or evaporation.

  Also, an anti-oxidation layer, such as a thin layer of evaporated gold, may be deposited on the top and bottom contacts to prevent oxidation. This layer may diffuse into the filler material during brazing.

  In addition, a solder barrier similar to solder barrier 130 in FIG. 1 may be applied to improve the assembly process to PCBs and the like, or alternatively, it may be used for the electrode before brazing. It may be a part.

Another embodiment of the present invention is a method for manufacturing a battery or an electrochemical capacitor. In this embodiment, step e of the previous embodiment consisting of depositing a dielectric layer and step f of attaching the insulator are replaced by the next step.
m. Depositing anode 272 as depicted in FIG. 11 from the materials discussed above for the anode material.
n. Depositing a solid electrolyte 274 as depicted in FIG. 11 from the materials discussed above for the solid electrolyte.
o. Installing insulators 432 and 532; This step may be performed before step n with similar product performance.
p. Depositing cathode 276 as depicted in FIG. 11 from the materials discussed above for the cathode material. Note that this step and step m can be interchanged with similar product performance.

  In another embodiment, an electrochemical capacitor or battery is manufactured without depositing conductors 408, 508 and plugs 416, 516, and anode 272 and cathode 274 provide current to pore length in addition to battery electrode function. It plays the function of guiding along.

  Low leakage current is a significant problem for useful capacitors, batteries or electrochemical capacitors. Such leakage current is limited by utilizing an ALD deposition process to deposit dielectrics 412, 512 in the case of capacitors or solid electrolyte 274 in the case of batteries or electrochemical capacitors. ALD is well known to achieve a very conformal coating without pores or defects, which allows a good quality layer with a small number of molecular layers.

  The current design of the capacitor compared to the electrolytic capacitor has better reliability, wide range of operating temperature, long life, bipolar operation, non-contamination on failure, better capacitance accuracy, better parameters There are other advantages such as good temperature stability, resistance to voltage spikes, etc. Benefits to electrochemical capacitors and batteries include short ion transport distances, fast charge / discharge and others.

Low series resistance is also a major concern for useful capacitors, batteries or electrochemical capacitors. Computing the series resistance of the capacitor includes coupling the conductor and plug layers in parallel. By way of example but not limitation, it is assumed that the capacitor was made from 1 × 1 × 1 mm 3 nanoporous Al 2 O 3 with an average pore diameter of 70 nm and 130 × 10 6 pores. The conductor layer is 6 nm thick, the insulating layer is 10 nm thick, and the plug diameter is a nominal 38 nm or 19 nm thick layer deposition. The capacitance as calculated in the previous embodiment example is 100 μF. It is further assumed that the conductors and plugs are made of TiN with 1000 μΩcm or 10-5 Ωm, which is the resistance achievable for the as-deposited layer and may be greatly improved by annealing or other techniques. To do. For ease of calculation, it can be assumed that the conductor tube has a thickness of 6 nm and an average diameter of 67 nm and has almost the same cross-sectional area as a 38 nm diameter plug. Resistance is
R = (10−5 × L [m] / S [m2]) / N
= (10-5 * 10 <-3> / ([pi] * (38 * 10 <-9>) 2/4)) / 130 * 106
= 7 × 10-2Ω = 70mΩ
It is.

  It is well known that a tantalum electrolytic capacitor having a capacitance of 100 μF has a series resistance of 0.9 to 1.5Ω. Accordingly, materials with poor conductivity may be used for the conductors and plugs for superior performance that improves beyond the performance of currently available electrolytic capacitors.

  The inductance will be very low due to the almost linear flow of current and the impedance is expected to remain the same up to very high frequencies, similar to multilayer ceramic capacitors. Thus, in contrast to current practice of installing a ceramic capacitor next to each electrolytic capacitor, such practice is not required for capacitors 400,500.

  For electrochemical capacitors or batteries, the short ion transport distance 278 of ions in the electrolyte as shown in FIG. 11 is basically a radial movement in the pores over a distance of tens of nanometers. The time required for ions to move from the anode to the cathode and back is reduced, and there is also a reduction in series resistance and an increase in the maximum allowable charge / discharge current compared to a conventional electrochemical capacitor or battery.

  It should be understood that variations of the structural assembly are possible. For example, in another embodiment, the top contact is deposited directly on one side of the scaffold, for example by sputtering. The upper terminal is then brazed to this upper contact. The conductor is then ALD deposited and the dielectric is ALD deposited. The insulator is then attached and then the plug is ALD deposited. Finally, the bottom contact is deposited in the same manner as the top contact and the bottom terminal is brazed. Another variation is as follows, where the top contact is deposited directly on one side of the scaffold, for example by sputtering. The upper terminal is then brazed to this upper contact. The conductor is then ALD deposited. The insulator is then attached, the dielectric is ALD deposited, and then the plug is ALD deposited. Finally, the bottom contact is deposited and the bottom terminal is brazed.

  In another embodiment, the anodized nanopore scaffold is made of an aluminum structure that has a layer of different metal that stops the anodization process and allows the pores to end directly with different metals. If a different metal is not oxidized by the electrolyte, the dried scaffold will already have a built-in upper terminal. The conductor is then ALD deposited and the dielectric is ALD deposited. The insulator is then attached and then the plug is ALD deposited. Finally, the bottom contact is deposited and the bottom terminal is brazed.

  The foregoing discussion has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. For example, in the foregoing “detailed description”, the various features of the invention are grouped together in one or more embodiments for the purpose of simplifying the invention. This method of invention should not be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. On the contrary, the inventive aspects lie in less than all of the single previously disclosed embodiments, as reflected in the following claims. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the invention.

  Although various embodiments of the present invention have been described in detail, it will be apparent to those skilled in the art that changes and modifications in those embodiments may occur. However, it should be clearly understood that such changes and modifications are within the spirit and scope of the invention as set forth in the following claims.

DESCRIPTION OF SYMBOLS 100 Sintered capacitor 104 Sintered metal 112 Dielectric 118 Electrode 124 Filler 128 Bottom terminal 130 Solder barrier 132 Insulator 140 Filler 144 Top terminal 200 Capacitor 204 Scaffold 206 Pore 208 Conductor 212 Dielectric 216 Plug 224 Filler 228 Bottom terminal 232 Insulation Body 240 Filler 244 Upper terminal 272 Anode 274 Solid electrolyte 276 Cathode 278 Ion transport distance 300 Capacitor 301 Carrier 304 Scaffold 306 Pore 308 Conductor 312 Dielectric 316 Plug 324 Filler 332 Insulator 350 First conductive region 352 Second conductivity Active region 354 Top material layer 400 Battery or electrochemical capacitor 404 Scaffold 408 Conductor 416 Plug 412 Dielectric 420 Bottom contact 424 Bottom filler 428 Bottom terminal 432 Insulator 436 Top contact 440 Top filler 444 Top terminal 500 Capacitor, battery, or electrochemical capacitor 504 Scaffold 508 Conductor 512 Dielectric 516 Plug 520 Bottom contact 524 Bottom filler 528 Bottom terminal 532 Insulator Contact 540 Upper filler 544 Upper terminal

Claims (54)

In a method of manufacturing an electrical component,
Providing a scaffold having a plurality of pores therein, wherein the plurality of pores are at least two non-overlapping surfaces, a first surface of the scaffold, and a second surface of the scaffold. Ending with at least one pore of the plurality of pores traversing the scaffold from the first surface of the scaffold to the second surface of the scaffold;
Depositing a first conductor layer on a surface of the scaffold including conformally to the inner surface of the plurality of pores;
Depositing one or more material layers on the first conductor layer including conformally to the inner surfaces of the plurality of pores;
Depositing a second conductor layer on the one or more material layers including conformally to an inner surface of the plurality of pores;
Providing a first electrical contact region on a first surface of the scaffold at the first surface of the scaffold;
Providing a second electrical contact area on a second surface of the scaffold at the second surface of the scaffold.   The method of claim 1, wherein the at least one deposition step is performed by atomic layer deposition (ALD).   The method of claim 1, wherein the scaffold comprises a sintered metal material and at least two pores of the plurality of pores intersect each other.   The plurality of pores are generally linear, and the first surface of the scaffold is a region of the scaffold where a first end of the pore ends, and the second of the scaffold. The method of claim 1, wherein a surface is a region of the scaffold where the second end of the pore ends.   The method of claim 1, further comprising attaching an insulator, wherein the first electrical contact region is separated from the second electrical contact region by the insulator. Attaching a first terminal to the first electrical contact area;
The method of claim 1, further comprising attaching a second terminal to the second electrical contact region.   The method of claim 1, further comprising providing a carrier that supports the scaffold on the first electrical contact area.   The method of claim 1, wherein the one or more material layers are dielectric layers.   A capacitor manufactured by the method according to claim 8.   The method of claim 1, wherein the one or more material layers are cathode, solid electrolyte and anode layers.   A battery manufactured by the method according to claim 10.   An electrochemical capacitor manufactured by the method according to claim 10. A perforated scaffold having a plurality of pores therein, the pores ending with at least two non-overlapping surfaces, a first surface of the scaffold, and a second surface of the scaffold; At least one pore of a plurality of pores, the perforated scaffold traversing the scaffold from the first surface of the scaffold to the second surface of the scaffold;
A first conductor layer and a second conductor layer, the first conductor layer being at least two conductor layers substantially conformal to the surface of the pores in the scaffold, wherein the first conductor layer comprises the first conductor layer; At least two conductor layers having no direct electrical contact with the two conductor layers;
A first electrical contact area disposed on a first surface of the scaffold at the first surface of the scaffold;
An electrical component comprising: a second electrical contact region disposed on a second surface of the scaffold at the second surface of the scaffold.   The electrical component according to claim 13, wherein the scaffold includes a sintered metal material, and at least two pores of the plurality of pores intersect each other.   The plurality of pores are generally linear, and the first surface of the scaffold is a region of the scaffold where a first end of the pore ends, and the second of the scaffold. The electrical component of claim 13, wherein a surface is a region of the scaffold where the second end of the pore ends.   The electrical component of claim 13, further comprising a carrier on which the scaffold is mounted at the first electrical contact region.   The electrical component of claim 13, further comprising an insulator separating the first electrical contact region from the second electrical contact region. A first terminal attached to the first electrical contact region;
The electrical component according to claim 13, further comprising a second terminal attached to the second electrical contact region.   The electrical component according to claim 13, further comprising a dielectric layer disposed conformally in the pores between the first conductor layer and the second conductor layer.   The capacitor according to claim 19.   The electrical component of claim 13, further comprising a cathode, a solid electrolyte, and an anode layer conformally disposed in the pores between the first conductor layer and the second conductor layer.   The battery according to claim 21.   The electrochemical capacitor according to claim 21. In a method of manufacturing an electrical component,
Providing a scaffold having a plurality of pores therein, the pores ending at at least two non-overlapping surfaces, at a first surface of the scaffold, and at a second surface of the scaffold. At least one pore of the plurality of pores traverses the scaffold from the first surface of the scaffold to the second surface of the scaffold;
Depositing a layer of conformal anode, solid electrolyte and cathode on the scaffold including within the interior surfaces of the plurality of pores;
Providing a first electrical contact region on a first surface of the scaffold at the first surface of the scaffold;
Providing a second electrical contact area on a second surface of the scaffold at the second surface of the scaffold.   25. The method of claim 24, wherein at least one deposition step is performed by atomic layer deposition (ALD).   25. The method of claim 24, wherein the scaffold comprises a sintered metal material and at least two pores of the plurality of pores intersect each other.   The plurality of pores are generally linear, the first surface is a region of the scaffold where a first end of the pore ends, and the second surface is the pore. 25. The method of claim 24, wherein the scaffold is the region of the scaffold ending at the second end of the scaffold.   25. The method of claim 24, further comprising attaching an insulator, wherein the first electrical contact region is separated from the second electrical contact region by the insulator. Attaching a first terminal to the first electrical contact area;
25. The method of claim 24, further comprising attaching a second terminal to the second electrical contact area.   25. The method of claim 24, further comprising providing a carrier that supports the scaffold on the first electrical contact area.   A battery produced by the method of claim 24.   25. An electrochemical capacitor produced by the method of claim 24. A perforated scaffold having a plurality of pores therein, the pores ending with at least two non-overlapping surfaces, a first surface of the scaffold, and a second surface of the scaffold; At least one pore of a plurality of pores, the perforated scaffold traversing the scaffold from the first surface of the scaffold to the second surface of the scaffold;
An anode, a solid electrolyte and a cathode layer disposed conformally on the scaffold including within the inner surfaces of the plurality of pores;
A first electrical contact area disposed on a first surface of the scaffold at the first surface of the scaffold;
An electrical component comprising: a second electrical contact region disposed on a second surface of the scaffold at the second surface of the scaffold.   34. The electrical component of claim 33, wherein the scaffold comprises a sintered metal material, and at least two pores of the plurality of pores intersect each other.   The plurality of pores are generally linear, the first surface is a region of the scaffold where a first end of the pore ends, and the second surface is the pore. 34. The electrical component of claim 33, wherein the electrical component is an area of the scaffold that ends at a second end of the scaffold.   34. The electrical component of claim 33, wherein the scaffold further comprises a carrier mounted thereon at the first electrical contact area.   34. The electrical component of claim 33, further comprising an insulator that separates the first electrical contact region from the second electrical contact region. A first terminal attached to the first electrical contact region;
34. The electrical component of claim 33, further comprising a second terminal attached to the second electrical contact region.   34. A battery according to claim 33.   34. An electrochemical capacitor according to claim 33. In a method of manufacturing an electrical component,
Providing a sintered metal scaffold having a plurality of pores therein, wherein the scaffold material is hardly oxidized.
Providing a first electrical contact area on a first surface of the scaffold;
Using ALD to conformally deposit a material layer on the surface of the scaffold including the inner surfaces of the plurality of pores;
Providing a second electrical contact area on the second surface of the scaffold;
Attaching an insulator separating the first and second electrical contact regions;
The method wherein the first surface and the second surface do not overlap. Attaching a first terminal to the first electrical contact area;
42. The method of claim 41, further comprising attaching a second terminal to the second electrical contact area.   42. The method of claim 41, wherein the material layers are a dielectric layer and a conductor layer.   44. A capacitor manufactured by the method of claim 43.   42. The method of claim 41, wherein the material layer is a cathode, solid electrolyte, and anode layer.   46. A battery manufactured by the method of claim 45.   46. An electrochemical capacitor produced by the method of claim 45. A sintered metal scaffold having a plurality of pores therein;
A material layer disposed on a surface of the scaffold and conformal to the surface of the scaffold including the inner surfaces of the plurality of pores;
A first electrical contact region disposed on a first surface of the scaffold and in electrical contact with the scaffold;
A second electrical contact region disposed on the second surface of the scaffold and in electrical contact with one of the material layers;
An insulator separating the first and second electrical contact regions;
The electrical component wherein the first surface and the second surface do not overlap. A first terminal attached to the first electrical contact region;
49. The electrical component of claim 48, further comprising a second terminal attached to the second electrical contact region.   49. The electrical component according to claim 48, wherein the material layer is a dielectric layer and a conductor layer.   51. A capacitor according to claim 50.   49. The electrical component of claim 48, wherein the material layer is an anode, solid electrolyte, and cathode layer.   53. A battery according to claim 52.   53. An electrochemical capacitor according to claim 52.

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