KR20150079749A - Laminated materials, methods and apparatus for making same, and uses thereof - Google Patents

Abstract

PVD methods and apparatus for producing materials such as, for example, nitrides are disclosed, and such materials are electrode materials.

Description

TECHNICAL FIELD [0001] The present invention relates to a laminate material, a method and an apparatus for producing the same, and a laminated material,

The present invention relates to laminated materials, methods and apparatus for making same.

In the following description, reference is made to the use of III-V semiconductors. In particular, without limitation, the use of nitrides is referred to, but it will be understood by those skilled in the art that the invention is not limited to such use. The present invention is directed to the invention as filed in United States Patent Application No. 61/540558 and PCT / EP2012 / 069156 (WO / 2013/045596). These applications are incorporated by reference to the extent permitted by the patent law.

The present invention is directed to applying the process contents disclosed in WO / 2013/045596 to make a laminate material. Such a laminating material allows the use of AIN's high thermal conductivity or other deposition materials to form a substrate for the thermal spreader on which the device is mounted.

In a first aspect, the present invention provides a laminate of an adhesion coating in a flexible substrate.

In a second aspect, the invention provides an apparatus for making a laminate material by vapor deposition, using an ion beam generator, as described herein.

In a third aspect, the present invention provides an electrode for an electrochemical device such as a battery, wherein at least one active layer is an adhesion layer formed by vapor deposition. The scope of the invention is defined by the claims.

In the following non-limiting description, reference is made to the figures.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic drawing of an apparatus, which can be used according to one aspect of the present invention and is disclosed in WO / 2013/045596.
2 is a schematic diagram of a plasma generator usable in the apparatus of FIG. 1;
FIG. 3 is a schematic diagram of a steam generator usable in the FIG. 1 apparatus. FIG.
Fig. 4 is a schematic view of the Fig. 1 apparatus and associated apparatus; Fig.
Figure 5 schematically illustrates a modification of a first device in accordance with one aspect of the present invention.
6 is a schematic view of a laminate material according to the present invention.
Figures 7 and 8 are schematic diagrams illustrating the use of the laminate product of Figure 6;

For the definition of terms in the following:

Relative position related terms such as " top, "" bottom" and "bottom" are understood to represent the relationships shown in the drawings and are not intended to limit the scope of the invention.

The term "condensed phase" will be interpreted to refer to a solid, liquid, or mixture thereof.

"Ion beam" refers to the flow of a gas / plasma material that includes ions and also includes neutral materials.

"Flexible" means that it can be bent or flexed without breaking, and can be bent to have a radius of 5 meters or less without being particularly destroyed.

"Comprising" is interpreted to include two meanings of "comprise" and "include, contain, embrace ". When used in connection with a single purpose, the term does not exclude the presence of other objects, and when used in connection with a list, the term does not imply that such a list is exclusive.

PVD  Explanation of methods and devices

The overall concept of the PVD device of WO / 2013/045596 is as follows:

One or more steam generators capable of forming steam in the state of one or more condensed materials;

One or more plasma generators comprising one or more cathodes (anodes) with one or more open-end channels, said channels having one or more channel walls and having a length extending from one end of the channel to the other end of the channel, Providing a plasma generator capable of forming a plasma in at least one of such spaces;

The at least one steam generator and at least one plasma generator are arranged such that steam generated by the steam generator during operation traverses the at least one space through a plasma created by the at least one plasma generator.

A portion of the steam traversing the neutral plasma; Some will be ionized and added to the plasma while traversing the plasma. After crossing the plasma, the vapor will collide with the substrate to form a composition.

1 to 4 PVL  Examples of devices

The apparatus 100 is shown in Figure 1 and is shown with the associated apparatus in Figure 4 and comprises an upper chamber 101 and a lower chamber 102 and the lower chamber includes an upper chamber 101 and a lower chamber 102 By a partition wall 103 having a hole 104 communicating with each other. The upper chamber 101 and the lower chamber 102 may be separated to allow access to the interior and optional means for access (e.g., door or port) may be devised by those skilled in the art of vacuum technology have.

Below the hole 104 is a vacuum generator 105 (shown in detail in FIG. 3). The upper chamber 101 has a plasma generator 106 (a useful form of the plasma generator 106 is shown in detail in Figure 2) and a substrate mount 107 on which the substrate 108 is mounted.

표면 및 코팅 기술 86-87 (1996) 648-656)가 사용되어 한 공간을 제공할 수 있으며, 그 같은 공간 내에서 플라즈마가 발생될 수 있다. The plasma generator 106 includes a space 110 in which a plasma 111 is generated and such plasma extends out of the space 110. [ The depicted plasma generator 106 is in the form of an annulus, but may have other structures (e.g., opposite plate cathode (anode), spiral cathode (anode) Radio frequency hollow cathodes for the plasma processing technology ,

Surface and Coating Technology 86-87 (1996) 648-656) can be used to provide one space, and a plasma can be generated within that space.

In WO 2009/092097, a concentric hollow cathode (anode) device is referred to, in which the hollow cathode (anode) annular core acts as a sputtering target. The device of WO2009 / 092097 is not suitable for use in the present invention as described below.

Plasma is generated from the gas being introduced into the upper chamber 101 (for example, through the gas inlet 112). An optional gas cleaner 113 may be provided in the chamber to reduce the content of oxygen and water vapor in the chamber. Depending on the gas used, the gas cleaner 113 may include a cooling trap and / or a getter. Examples of cooling traps include Meissner traps where liquid nitrogen is used to collect oxygen and / or water. (However, a Meissener trap is generally not useful when it is an ammonia nitrogen source.) For example, an example of an oxygen getter includes a magnetron sputter source of reactive metal used to get oxygen and moisture from the process chamber. Suitable reaction metals include Ti, Zr, Hf, or Y.

The steam generator 105 and the plasma generator 106 are arranged such that the steam 114 generated by the steam generator 105 traverses the plasma 111 when both of them are operating.

Figure 2 illustrates a useful form of the plasma generator 106, but the invention is not limited to the particular geometry shown in the drawings. An annular cathode (anode) backing 115 that is cooled by water (cooling by water is not shown) receives an annular cathode (anode) facing 116, Creating a space 110 to be created. As shown, the space 110 is cylindrical and has a constant length (from one open end to the other open end of the channel) and a diameter. The cathode (anode) sheath 116 may be made of any suitable material, but any element sputtered from the cathode (anode) sheath 116 will not contaminate such material, . ≪ / RTI > For example, when making the AIN, it may be useful to have aluminum (such as six Nine Pure Al, for example) in the cathode (anode) enclosure.

The two rows of magnets 117 are received between the cathode (anode) backing 115 and the cathode (anode) sheath 116. One row of magnets has an Arctic exterior facing inward and the other row has an Antarctic exterior facing inward. The resulting flux 118 may be applied to a cathode (anode) enclosure 116 (e.g., a 50%, 60%, 70%, 80%, or 90% ). A yoke (not shown) joins the end of the magnet 117 away from the cathode (anode) sheath 116 so that the magnet 117 is magnetized together with the yoke and magnetic flux 118 in the space 110 Thereby forming a part of the circuit. It is evident that more than one electrical magnet can provide the same effect.

The cathode (anode) housing 119 is electrically separated from the cathode (anode) backing 115 and the cathode (anode) housing 116 and includes a cathode (anode) backing 115 and a cathode (anode) (Cathode), and prevents plasma from being formed outside the cathode (anode) backing 115. As shown in FIG. Conveniently, the cathode (anode) housing 119 is separated from the cathode (anode) backing 115 to form a so-called dark space 120. The "dall space" is a small, narrow space compared to the average free path of electrons at the operating pressure, resulting in no plasma discharge between the housing 119 and the cathode (anode)

The plasma is confined only to the surface of the cathode (anode) enclosure 116, thus eliminating gas ionization: the electrons from the cathode (anode) arrive at the cathode (anode) housing without stimulating the arc within the dark space.

It is possible to use without the cathode (anode) housing and the wall of the upper chamber 101 as the anode (cathode). However, such a configuration would result in undesirable generation of unwanted stray plasma and deposition material if the chamber walls could not be used for dark space shielding.

Figure 3 shows a steam generator 105 usable in the present invention. Steam generator 105 may include an electron beam generator 105 that directs the electron beam to a condensed phase source of material, such as, for example, a first component of a composition to be deposited on substrate 108 . The steam generator includes a depression 134 on the top surface to accommodate the housing 135. An electronic gun (not shown) is located under the steam generator and a magnet (not shown) operates to bend the electron beam 136 from the transfer gun to impact the material held within the housing 135. Such a steam generator is known, and a suitable apparatus is the Temescal Corporation Model SFIH-270-2.

Figure 4 shows the device of Figure 1 with associated equipment. The lower chamber 102 has a conduit 109 connected to a vacuum pump 122 (e.g., Edwards Model 30) through a gate valve 121. To measure pressure in the system, pressure gauges 137 and 138 are connected to the lower and upper chambers 102 and 101, respectively. The pressure gauges 137, 138 may be any suitable type in which pressure and gas can be measured.

Typically, in the case of a pressure gauge 137, an ion gauge can be used and experienced as a pressure of about 10 ^-6 to 10 ^-3 Torr (such a gauge can be controlled, for example, by a Granville Phillips Model 270) .

 A baratron (e.g., MKS Model 125AA) is used for the pressure gauge 138 and the measured pressure is higher than the lower chamber. The present invention is not limited to a specific pressure measurement method.

Such a device with a lower pressure in the lower chamber will work best at low pressure and lower pressure in the lower chamber will prevent high voltage arcing from filament to ground, Allowing a sufficient gas pressure in the chamber 101 so that a hollow plasma generator can efficiently ionize a gas containing nitrogen.

One shutter may be installed between the upper and lower chambers for selective operation when it is determined that the metal vapor will coat the hollow cathode (anode) surface with metal prior to application of gas and plasma generation.

The cathode (anode) backing 115 (shown in FIG. 2) of the plasma generator 106 is attached to a voltage supply, which in the illustrated embodiment is connected to an RF generator 123 (e.g., Dressler Model CESAR) And is attached through the matching network 124.

The barrier 103 may be a steel or soft magnetic material and is optionally connected to a cathode (anode) housing 119 (shown in FIG. 2) to provide magnetic shielding so that the magnetic field of the plasma generator 106 is applied to the steam generator &(105); And in particular the magnetic field of the plasma generator 106, to prevent interaction with the electron beam 136.

The substrate mount 107 is in the form of a chuck that is heated by electrical resistance supplied from a power source 125 (e.g., Eurotherm SCR 40) and is mounted on a thermocouple 127 measuring the temperature of the substrate mount And is controlled by a connected power controller 126 (e. G. Eurotherm Model 1226e). Such devices of the heated substrate mount, power supply, and power controller allow the substrate mount, and thus the temperature of the substrate, to be maintained at a desired value.

The measurement of substrate surface temperature (e.g., by high temperature measurement of the surface of substrate 108) can provide suitable control, especially when the substrate is thick. The substrate 108 is secured to the substrate mount 107 by three spring-loaded pins (not shown), although other suitable means may also be used.

A second RF generator 128 (e.g., a Dressler Model CESAR) is attached to the substrate mount 107 via a second matching network 129 (e.g., Dressler Model CESAR).

The unit flow controller 130 (e.g., Unit Instruments Model UFC 1000) controls the supply of gas 131 to the gas inlet 112 (shown in FIG. 1).

A shutter 132 is provided between the plasma generator 106 and the substrate mount 107. Contamination and vapor are prevented from being deposited on the substrate 108 by the shutter 132. The shutters also prevent evaporation from the substrate to the hollow cathode (anode) during plasma etch cleaning of the substrate prior to deposition, and deposition is conducted from the hollow cathode (anode) to the substrate while the hollow cathode (anode) plasma reaches equilibrium Thereby preventing deposition.

The shutter 132 is provided with a periscope for internal examination of the apparatus described below.

The steam generator power supply 133 provides power to the steam generator 105.

1 to 4 Typical operation of the apparatus

Such a device may be operated with the following steps, modifications to these steps are possible, and still achieve the objects / features of the present invention. The substrate 108 may be mounted to the substrate mount 107 and a compressed state source of material (e.g., gallium or aluminum, alloys thereof, or other desirable components) may be placed in the housing 135. The shutter 132 may be positioned between the plasma generator 106 and the substrate 108. The system is pumped to vacuum the upper and lower chambers 101, 102. At this stage, the typical pressure in the chamber is about 10 ^-6 Torr, and above these pressures may be used.

Once the pressure drops, the following can be performed:

The power supply 125 is turned on to allow heat to the substrate mount 107, and then to the substrate 108, to reach the proper temperature for the desired product. For example, for the deposition of crystals, AlN 850 ° C may be used, other temperatures may be used, and the appropriate temperature depends on the substrate and the material to be deposited.

The RF generator 128 is turned on to supply RF to the substrate mount 107, then substrate 108 (generating a DC bias as is commonly known), and argon is supplied to at least one gas inlet 112 Into the chamber. RF power is applied in the upper chamber Archon (or other inert gas) pressure of 10 ^-3 to 5x10 ^-3 Torr, and is 50-100 watts and finally generates a substrate bias of 250 to 300 volts, the voltage of 300-400V can be used There are also.

This allows the substrate to reach the proper deposition temperature and allows the substrate to be cleaned by bombardment. The bombardment proceeds for 5 to 10 minutes. An inert gas other than argon (mold, Ne, Kr or Xe) may be used in the cleaning step and may be a mixture of inert gases. The argon supply is then shut off and RF generator 128 is turned off.

The vacuum generator power supply 133 is then turned on and the electron beam current is increased to begin heating the condensed phase source of the material. Often, this same purpose is to increase the condensed phase source temperature of the material to a temperature that is molten and has a useful high vapor pressure for deposition, without splashing the material into an oxidizing boil or gas discharge of impurities or trap gases .

It is useful to be able to observe the condensed phase source of such a material to ensure proper heating. For example, if the steam generator is an electron beam device (as shown in Figure 3), it may be useful to observe that the electron beam impinges on the condensed phase source of material to ensure proper alignment. A periscope located within the shutter and in the lower chamber 102 may be used for this purpose.

During such a heat treatment, surface contaminants on the condensed phase source of the material may be vaporized. Contaminants and vapors are suppressed or prevented from being deposited on the substrate 108 by the shutter 132. As the condensed phase source of the material melts, the contaminants generated on the condensed phase source of the material will either evaporate or sink to the edge of the molten material or float.

Other inert gases such as argon, or Ne, Kr, Xe or other elements may be injected through the material to be removed in the E-beam. Argon or other inert gases reduce the possibility of reactive gases reacting with the molten surface material. In the absence of an argon blanket for a generally molten surface material, AIN is formed at the surface to prevent AI vapor from leaving the molten surface, and AIN at such a surface is sputtered by E- From the E-beam source to the substrate. Such a process may also be carried out with other source materials to protect the source material during melting and vaporization.

One or more reactive gases (e.g., N ₂ , NH ₃ , N ₂ H _{2 ,} or other hydrogenated nitrogen or nitrogen containing compound, for nitride production, a gas containing oxygen for oxide production, A single gas containing the required element or mixture of gases may be used to produce a mixture of fluorine-containing gases (e.g., oxynitrides)) may be introduced into the upper chamber through one or more gas inlets 112 have. Some argon may also be introduced into the reaction chamber to assist in the bombardment of the substrate 108, which may improve the properties of the deposited material.

An upper chamber 101 within the typical pressure is about 10 ^-4 to 10 ^-2 Torr (for example, 1x10 ^-3 to ^within 5x10 ^-3 Torr; 1x10 ^-3 to 2x10 ^-3 Torr; or 3x10 ^-3 to 5x10 ^{- 3} Torr). The pressure in the lower chamber 102 is less than the pressure in the upper chamber 101, and the magnitude is half the pressure in the upper chamber or between 1/5 and 1/10. For instance, the same pressure in the upper chamber and 1x10 ^-3 to 2x10 ^-3 Torr range, the lower chamber ^3x10? To 5x10 ⁴ and ^-4 Torr range, and these can be itgido other pressures and pressure differences may be used between the chamber .

The operating pressure of the steam generator may be 5 x 10 ^-4 Torr or less, the operating temperature of the plasma generator may be 1 to 2 x 10 ^-3 , and the vacuum rate may be > 1000 l / min. The reaction gas feed rate (if used) may be 2-5 sccm (or may be above or below this range) and the ball active gas feed rate for blanketing the molten source material may be, for example, 10 sccm or Or less. These are exemplary and other embodiments may be used for these ranges.

The upper chamber 101 is under pressure and the RF generator 128 is turned on to supply 15-25 watts and eventually an RF bias of 80-150 volts to the substrate mount 107 and thus to the substrate 108 ; And the RF generator 123 is turned on to supply RF to the cathode (anode) of the plasma generator 106. A typical bias for RF generator 123 is 350 volts.

The RF supplied to the steam generator initiates a plasma discharge 111 in the space 110 and eventually causes ionization of the gas which is directed toward either or both of the steam generator 105 or the substrate 108 110).

The steam 114 from the steam generator 105 can react with the ionizing gas in the plasma 111. For example, in the case of AL as source material and nitrogene as reaction gas, AIN begins to form at shutter 132. As soon as the shutter 132 is removed, the vapor 114 and / or the plasma 111 can reach the substrate and begin deposition at the substrate. Applying RF bias to the substrate eventually results in localized plasma generation and helps to bombard the surface of the deposition material. It is desirable that no bias be applied to the substrate for amorphous deposition.

The rate of deposition can be measured using a deposition monitor, such as, for example, Inficon Model U200. The deposition temperature is 100-1100 占 폚, depending on the substrate material, and the deposition rate is 0.1 to 60 占 퐉 / hour, but the present invention is not limited to these temperatures or deposition rates.

Once the deposition material has reached the required thickness or depth, the following is performed:

The shutter 132 is closed,

RF is supplied to the substrate mount 107 and the plasma generator 106 is turned off,

· All gases are shut off,

The heater to the substrate mount 107 is turned off,

The power to the vacuum generator is turned off (which is slowly carried out to remove the voids formed in the solid material)

Nitrogen is injected into the vacuum chamber until the vacuum chamber reaches atmospheric pressure,

The vacuum chamber is opened when the substrate temperature is 500 ° C or lower,

The substrate 108 is removed (optionally after cooling for a suitable period of time).

The above description has been made using the apparatus shown. The apparatus can be used in other ways depending on the nature of the material to be deposited. For example, the composition of the gas may vary during processing, and the composition of the vapor may vary depending upon the choice of the optional vapor source. The adjustments to the processing can be automated by computer controls using National Instruments LabVIEW.

Specific examples of deposition processing

Comparative Example 1

A comparative example of the present invention is described from WO / 2013/045596.

Aluminum nitrides are made by placing pure Al (5 purity) in the device housing of Figures 1-4. The silicon substrate was fixed with the substrate mount. A substrate 108, which may be Si or other material, is mounted to the substrate mount 107 and is typically heated to 850 占 폚. (Typically, the substrate is heated to a temperature below the melting or deposition temperature of the substrate material, Wrapping should be avoided if the temperature is far below the melting temperature of the substrate material and the expansion coefficient of the substrate and film is completely different, such as 20% or more or 30% or more.

Typically, a typical substrate temperature is 250-1000 ° C, depending on the substrate material and depending on the required crystallinity of the deposited material (e.g., AIN). Typical temperatures for the deposition of AIN on various substrates include 300 ° C + 50 ° C for copper and aluminum deposition and 800 ° C + 50 ° C for deposition on Si, SiC, and aluminum oxide (sapphire).

The present invention is not limited to these temperature ranges or materials and another example of suitable material is provided in the examples below.

NH ₃ , N ₂ and Ar gases are conducted to the upper chamber 101 by gas inlet 112 (typical rates are 50% NH ₃ , 35% N ₂ and 15% Ar). The pressure in the upper chamber 101 is observed to be approximately 3-5 x 10 ^-3 Torr and the pressure in the lower chamber 102 is observed to be approximately 3-5 x 10 ^-4 Torr and optionally the pressure in the upper chamber is approximately 1 ^-5 x 10 ^-3 Torr, and the pressure in the lower chamber was observed to be approximately 1-5 x 10 ^-4 Torr.

The growth rate shown is> 40 μm / hour and sometimes> 80 μm / hour. The XRD of the deposited material is hexagonal AIN.

After this process, AIN has been successfully applied to Si, Al, sapphire, Mo, W, Nb, Ta, SiC, diamond, Cu and Ta phases without any peeling or cracking in the machine. Lt; / RTI > The deposited AIN film was transparent.

Comparative Example 2

A metal or graphite or diamond sheet, or housing, was attached to the substrate mount on an electron beam hearth in the same vacuum chamber. Chuck directed down toward the electron beam hearth. The vacuum chamber was typically vacuumed to < 5 x 10 ^-6 Torr and filled with argon at 3 x 10 ^-3 Torr. The RF generator is attached to the substrate mount, for example at 13.56 M Hz, and is turned on for 100 minutes for 10 minutes to clean the substrate. The RF generator is turned off and the vacuum chamber is again pumped down to <5 × 10 -6 Torr. The substrate mount temperature was increased to 800 ° C. The electron beams were turned on to melt Al and the deposition rate was set to 0.3 nm / sec. This rate can be increased at the rate described herein by increasing the power of the electron beam. Ar was turned on at ~ 3 SCCM and NH3 generated a vacuum pressure of ~ 6 x 10-4 Torr as measured in the lower chamber.

The RF generator attached to the hollow cathode (anode) was turned on, a plasma was generated, and N ₂ was ionized. The RF generator attached to the substrate mount was also turned on and a self bias of 120-140 volts was generated on the substrate. This bias causes the Ar ions to bombard the deposited AIN, resulting in very dense crystalline films.

Next, the shutter between the electron beam gun and the housing was opened. The shutter was opened for 15 minutes. The shutters were usually open for 15 minutes, resulting in 15 [mu] m of AIN deposition. The shutter was closed and the electron beam was blocked, the RF generator was turned off and the gas was shut off. The chuck heater was turned off. When the chuck reached 500 ° C, the vacuum chamber was again filled with N ₂ at atmospheric pressure. The vacuum chamber was opened and the metal or graphite or diamond sheet, or housing, was removed.

The resulting AIN coating had good adhesion to metals, graphite and diamonds and allowed the coated substrate to thermally cycle to 1100 占 폚 without cracking or peeling of the AIN. The graphite substrate with a 5 탆 AIN coating was thermally cycled at 1100 캜 and the quality of the AIN film did not deteriorate. In the diamond-coated silicon substrate and heated to 1100 C ^O 15㎛ film did not show any degradation of the AIN film. Such AIN coatings, high thermal conductivity materials can be used in thermal management. This process is explained next.

AIN was deposited to a thickness of 15 μm with Cu without any cracking or peeling of AIN.

AIN was deposited to a thickness of 15 μm with diamond without any cracking or peeling of AIN.

AIN was deposited in a thickness range of 100 nm to 150 μm with a silicon wafer without any cracking or peeling.

Example  One

A 5 탆 thick layer of AIN was coated with a 0.15 mm (0.005 inch) thick sheet of Ta using the apparatus and method of Comparative Example 1, and the sheet thus coated with Ta was then coated with a 0.375 inch diameter It was rolled into a tube. No peeling or cracking of AIN was observed.

These materials are considered very flexible. As described hereinabove, flexible means that it can be bent without breaking, which means that it can be bent into a previous shape having a radius of 5 meters or less without breaking. With an appropriate choice of material and thickness, the substrate, or both the substrate and the coated substrate, may be less than or equal to 1 meter, or 50 cm or less, or 20 cm or less, or 10 cm or less, or 5 cm or less, It can be bent without being broken.

In the present invention, the intermediate region may be between the deposited material and the substrate. Such an intermediate region may have a different composition or structure than the deposited material or the substrate itself. Such an intermediate region may be one or more components forming the deposited material and one or more components forming the substrate.

Such an intermediate region can occur through the reaction at an early stage of deposition and has a remaining thickness of deposited material formed thereon; Or it may be a separately applied layer, which may optionally have a different chemical composition from either the substrate or the deposited material.

Figure 6 shows an example of a design with layers. In Fig. 6 (not by actual scale), the laminate 400 is shown. The substrate 401 has one layer 402 attached to the substrate surface. The layer 402 has an intermediate region 403 sandwiched between the deposited layer 405 and the substrate 401. The intermediate region 403 may have a different composition or chemical composition from the deposited layer 405. The intermediate region 403 may be a reaction product (product) of one or more components forming the film 405 and one or more components forming the substrate 401.

As an example, without limiting the invention, the substrate 401 may be a flexible material, such as, for example, copper, the film region 405 may be AIN, and the middle region 403 may be one or more Components, aluminum, nitrogens, and / or aluminum nitrides.

The present invention contemplates both the intermediate layer formed through reaction with the substrate, and the intermediate layer intentionally formed. Such a laminate can be used as a heat sink for thermal management.

As an example, aluminum nitride, such as films deposited on flexible substrates such as metal, ceramic, glass or even plastic flexible substrates, can provide excellent thermal management characteristics due to the aluminum nitride characteristics. For example, the film may have a thermal conductivity of 210 W / mK to 319 W / mK, such as 210-275 W / mK or 210-250 W / mK.

The aluminum nitride located on the substrate may have one or more of the following additional characteristics.

The thermal management may be an electronic device such as a CPU, a light emitting device (e.g., LED), a cellular phone, a smart device, and the like. For example, the laminate 400 can comprise a layer of material attached to a substrate, and either or both of such layers and plates can be made of a high thermal conductivity material.

For example, a material such as aluminum nitride attached to a metal substrate, such as copper, may be applied to a printed circuit board (PCB) or mount (or submount) that is typically made of a polymeric material or resin and is not a good conductor, As a heat sink. Other substrates with high thermal conductivity can include, for example, other metals, graphite, and diamonds without limitation.

In the context of the present invention, one or more chips, such as integrated circuits (ICs) or computer chips, may be laminated via interconnects or bumps, and due to the dielectric properties of the film (e.g., aluminum nitride) The bumps can be made of metal without the need for a separate insulating layer.

Alternatively, the laminar heat sink of the present invention may be located on a mount or a PC board, or may be a mount or a PC board itself.

As an example, the laminate heat sink of the present invention may be a heat sink for a light emitting diode device, wherein the die is located on a heat sink and, due to the dielectric properties of the film used for the inventive laminate heat sink, No separate isolator is required between the die and the heat sink.

Figures 7 and 8 illustrate examples of these characteristics. As shown in FIG. 7, the assembly 410 includes a mount or a PC board 413 together with the mounted IC chip 419.

The mount or PC board 413 may have a laminate 415 of the present invention located at the top and attached to the mount or PC board 413. [ Such a laminate 415 may comprise a substrate 416, which may be any substrate specified in the present invention, but in the present embodiment, such a substrate is a good thermally conductive substrate such as copper .

One layer 421 of aluminum nitride or other material with good thermal conductivity is placed on the substrate. Bumps 417 from IC or other electronic components are connected to layer 421 to secure chip 419 and provide good thermal conductivity.

8 illustrates that the laminates 415 of the present invention have a substrate 416 and a thermal conductive layer 421 and can be used as a mount or a PC board itself. One or more IC chips 419 are attached to layer 421 by bumps 417. [

Although bumps are shown in Figs. 7 and 8, other means for providing a good thermal conductivity, such as a metal or a high thermal conductivity layer, between the IC chip 419 and the layer 421 can be envisaged.

Edit Device

Optional device

In the apparatus embodiment of FIGS. 1-4, a single steam generator with a single space, and a single plasma generator, are described, but the invention is not limited to such an implementation. For example:-

Feeds to a plasma generator as long as the single steam generator has more than one space;

A single steam generator feeds one or more plasma generators having one or more spaces;

Feeds to a plasma generator as long as one or more steam generators have more than one space;

One or more steam generators feed to one or more plasma generators having one or more spaces.

In the exemplary apparatus of Figs. 1-4, a single substrate is shown mounted on a single and fixed substrate mount, although the invention is not limited to such an implementation.

In the present invention, the following can be considered:

A plurality of substrates mounted on a single substrate mount;

Movable substrate mounts (eg, rotatable or slide mounts);

Movable substrate mounts and air locks to enable removal of the substrate from the device while under vacuum.

Many techniques for handling substrates have been developed in the field of semiconductor processing and the present invention contemplates the use of all known techniques that may be usefully applied to the present invention.

The present invention is directed to depositing on a flexible substrate. Several modifications can be applied. Figure 5 shows an apparatus according to one aspect of the present invention, which includes forming a film on a roll of a flexible substrate for continuous or semi-continuous operation. 5, a flexible substrate roll 500, such as a copper roll, may be fed to the apparatus 100 and used as the substrate 108, wherein a film is deposited on the substrate To form a coated substrate or laminates 504, and then such laminates may be selectively rewound with the laminate rolls 502. The substrate can be supplied at a desired deposition rate and constantly or incrementally to a desired film thickness formed on the substrate 108. The apparatus of FIG. 5 may include all the features of the FIG. 1 apparatus, but other features may also be required.

The apparatus of FIG. 5 as described above will require the formation of a vacuum gate to prevent air access to the chamber 101. In an optional configuration, both the roll 500 and the laminate roll 502 may be received inside the upper chamber 101 or may be received within the removable chamber 510, 512 shown in dashed lines in Fig. 5, The lock is operable to close the removable chambers 510, 512 to allow loading or unloading of the roll 500 and the laminate roll 502, respectively.

An RF generator is provided in the selectively separated heating section to allow cleaning of the roll (or the flexible substrate when the roll is unfolded) before deposition.

In the case of AIN coatings, it is suspected that AIN is at least partially oxidized in heat treatment and may form an aluminum oxynitride layer, although it is not desired to be constrained to such an assumption. The present invention can be further modified by exposing the applied nitrided coating to an oxygen-containing material at elevated temperatures, but is not limited exclusively to AIN coatings. The material may be an oxygen containing gas or it may result from contact with liquid or solid oxygen containing reactants. In the case of AIN coatings, the present invention may allow oxidation to be part of the deposition process by inserting an oxygen-containing gas (e.g., O ₂ , H ₂ O, or nitric oxide) during the final stage of the deposition of AIN.

The present invention further considers complete oxidation of AIN to provide aluminum oxynitride through the coating. Reducing the surface roughness prior to coating helps to reduce defects in the coating.

The process described above can be used to produce a laminate article comprising one or more deposited layers on a flexible substrate. Although the metal in the examples is referred to as a potential substrate for the deposition of layers, the present invention includes deposition on all flexible substrates that have wider applicability and are capable of accommodating adherent deposition without substantial damage to the substrate.

Typically, the substrate may have a melting or decomposition temperature of 200 캜, or 300 캜 or 400 캜 or higher. The substrate can be a metal, glass, ceramic, glass ceramic, such as graphene, functional graphene, exfoliated graphite, or a carbon-based material, for example, Based material, such as a composite material, or a polymer. The substrate may be partially crystalline or amorphous. If a polymer is used, both thermosetting and thermoplastic polymers can be used, although thermosetting polymers are more preferred to prevent damage in processing.

Adherent deposition means deposition that does not exhibit any cracking or peeling when using a laminate article. This includes that no cracks or delaminations occur after the substrate with the deposited deposition is exposed to high temperatures. The high temperature is meant to be within 20% of the melting temperature of the substrate or layer (whichever is lower) after returning to a lower temperature (for example, 25 ° C). The adhesion can be checked by other methods (for example, cycling between low temperature and high temperature).

The deposited layer adhered to the substrate may have a low oxygen content when the oxide is not intended. For example, a metal or metal nitride or other non-oxygen containing layer can be deposited on the substrate, which has a low oxygen content. The oxygen content for such a layer can be from about 1 ppm to 299 ppm, or from 3 ppm to 100 ppm, or from 1 ppm to 100 ppm, or from 1 ppm to 10 ppm, and the like. Due to the process of the present invention, other impurities such as gas impurities and / or metal impurities can be very low. For example, if a vaporized source material having a very high purity such as 99.999% or 99.9999% is used, all other impurities (gas and / or metal or completely different impurities) in the film can be less than 10 ppm and less than 5 ppm And may be about 1 ppm or 1 ppm, such as between 1 ppm and 5 ppm.

In the present invention, the layer deposited on the substrate has good coating uniformity as low as +/- 5% of the total deposition surface of the substrate. In the present invention, voids or pinholes were not observed even at 300 X or 500 X magnification of the layer deposited on the substrate. The layer deposited in close contact with the substrate has a preferred thickness such as from 0.1 micron to 2 mm, from 0.1 micron to 1 mm, from 10 microns to 500 microns, from 10 microns to 100 microns, such as from about 0.1 microns to 2 mm or more.

Prior to having the deposited film, the substrate may be pre-treated with conventional techniques such as surface cleaning, acid treatment, surface polishing (e.g., electropolishing). These various cleaning or polishing steps can be performed using conventional techniques related to substrate materials. Similarly, after the film is deposited on the substrate, the laminates, which may have any shape, are subjected to a cleaning treatment, heat treatment at any of a variety of temperatures or pressures, or liquid or gas (selective room and / or high temperature and / Such as, for example, nitrogen and / or oxygen, halogen-containing gas and / or air at optional pressures.

The method of the present invention provides a deposition on a flexible substrate, but a thick coating can be applied, and the present invention is not limited to such flexible coating articles, although a flexible coating article is preferred.

The material made by the process described above may have a deposited layer having a composition different from that of the material. The material made by the above-described processing may be an electronic component; Optoelectronic components; Electroacoustic components; MEMS components; And / or a spintronic component. &Lt; RTI ID = 0.0 &gt; [0002] &lt; / RTI &gt; .

Electrode material

The present invention has realized that vapor deposition provides a method for the fabrication of novel electrode materials for use in electrochemical devices such as batteries. In the following description, reference will be made to the manufacture of an anode (cathode) for a lithium ion battery, but the present invention is not limited thereto.

Various types of lithium-ion batteries have achieved widespread use in a variety of applications. Most often seen in electronic articles such as cell phones, laptops, cameras and other handheld devices, they can also be seen in the use of power tools and are increasingly used in more demanding applications, from electric cars and airplanes to tugboats and yachts. do .

There are many desirable forms of use of lithium ion batteries in a wider variety of applications, while minimizing environmental impact; When an electric vehicle or a hybrid electric vehicle using a lithium ion battery is used in preference to a vehicle driven by a fossil fuel, which is a harmful air emission source, it may have a good influence on air pollution, smog, and climate change.

However, in order for such batteries to be used in a wide range of applications, these batteries must deliver power efficiently while keeping their production costs low. There is a need therefore for a method of improving the properties of a lithium-ion battery that can be implemented using inexpensive materials and simple techniques that are readily applicable in industry. Such an improvement should also consider the safety issue in both the design of the battery and the risks imposed on the user by the materials used to manufacture the battery.

Considering these points, the negative electrode (referred to as "anodes" in the following description) at the time of discharge contains carbon, especially graphite particles, because graphite is safe, has a high capacity for lithium ion storage , And is conductive. Usually anodes are made from a mixture of a carbon material and an electrically conductive additive (usually carbon black) and a binder.

Graphite is the preferred material for anode (cathode) production, but there are other materials with higher capacity for lithium than graphite. The most well known are Si, Sn, Sb, Ge and Al, but the irradiated materials include a metal and a compound that further forms another compound with lithium, or another compound with lithium.

The problem with these materials, however, is that they exhibit greater expansion and contraction as they absorb lithium and release the absorber, which causes mechanical failure of the material and thus reduces charge-charging efficiency.

It has been proposed to apply a layer of active material comprising an active material comprising a metal capable of forming an alloy with lithium and a binder resin to a copper foil (WO2011074439).

Applicants have discovered that applying an active material to a current collector using vapor deposition allows the adjustable application to the ash to provide an intimate contact coating of the active material, which tends to provide a low electrical resistance (impedance) in the electrode .

Thus, the present invention further provides a laminator for use as an electrode for a battery, wherein such a laminator comprises an electrically conductive layer operable as a current collector, and

At least one active layer comprising at least one solid state comprising at least one solid state that acts to absorb an element carrying a charge and to discharge an absorption in the operation of such a battery, wherein the at least one active layer is formed by vapor absorption And is an adhesive layer. The absorption and absorption discharge can be by physical absorption / absorption discharge or by temporary alloying or compound formation.

The at least one solid state is active to absorb lithium and release the absorption as a charge transport element. Absorption and absorption can be physical absorption / absorption emissions, or transient alloying or compound formation. Physical absorption includes absorption into the surface, absorption into the material, intercalation into small gaps in the material, or a combination thereof, which are referred to as "absorption ".

Absorption emission is the reverse process in which the charge transport element is released at the point where it is absorbed. Transient alloying or compound formation involves treatments such as ion exchange and includes intercalation into small gaps in the material to produce alloys or compounds.

The at least one solid state comprises one or more elements, alloys or compounds and allows the formation of an alloy or compound with lithium. The at least one solid state may be in the form of an element, an alloy, or a compound, such as B, Mg, Al, Si, Zn, Ga, Ge, As, Se, Pd, Ag, Cd, In, Sn, Sb, Au, Hg, Tl, Pb, and Bi.

The at least one solid state comprises one or more of the elements and an alloy of one or more other alloying elements. The one or more other alloying elements may comprise one or more elements forming part of the electrically conductive layer.

For example, the electrically conductive layer comprises copper and at least one solid state comprises alloy Cu6Sn5.

Alloys have a relatively low electrical conductivity in terms of lithium adsorption / desorption capacity (e.g., Si, Sn, Sb, Ge, Al) and have advantages in mechanical damage upon expansion / contraction. .

By providing an alloy having an electrically conductive and flexible element, the electrical conductivity can be increased and the resistance to mechanical damage can be reduced. Elements having both electrical conductivity and ductility are preferred.

One or more solid states may be combined with at least one element selected from the group consisting of B, Mg, Zn, Ga, As, Se, Pd, Ag, Cd, In, Te, Pt, Au, Hg, Tl, , &Lt; / RTI &gt; Sb, Ge, and Al.

The at least one solid state is at least one selected from the group of B, Cr, Nb, Cu, Zr, Ag, Ni, Zn, Fe, Co, Mn, Sb, Zn, Ca, Mg, V, Ti, In, Element and at least one element selected from the group consisting of Si, Sn, Sb, Ge, and Al.

The one or more other alloying elements may comprise one or more elements forming part of the electrically conductive layer. For example, the electrically conductive layer comprises copper, and one or more solid states may comprise alloy Cu6Sn5 or other alloy capable of alloying with lithium.

The active layer is not continuous and forms ridges and islands with empty gaps that can be filled with other materials or to contain electrolyte.

The electrically conductive layer may comprise a first electrically conductive layer and a laminate of one or more second electrically conductive layers that can absorb or release an electrical charge transport element during operation of such a battery.

One or more of the first conductive layer and the one or more second electrically conductive layers may absorb the charge transport element and emit the absorption during such battery operation. One or more layers capable of absorbing the charge transport element and releasing the absorption during operation of such a battery include at least one carbon anode (cathode) that allows absorption / emission of lithium.

In addition, the electrically conductive layer may comprise a laminate of one or more conductive layers having a non-conductive layer. For example, the electrically conductive layer may comprise one or more conductive layer laminates on a non-conducting or insulating carrier, which is a metallized plastic.

Example 2

Using the apparatus of Figs. 1-4, a 3 탆 thick silicon layer is coated with 100 탆 and 13 탆 thick copper foils to produce a laminate structure comprising silicon coating closely on copper. Such silicon wraps the copper foil due to the difference in thermal expansion coefficient. However, such coated copper foils could easily be compressed and flattened without silicon cracking or peeling.

This ease of flattening indicates that the coated copper foil will be able to withstand the expansion and contraction by absorbing and absorbing lithium by the silicon.

In this embodiment, direct lamination of the active layer (silicon) to the electrically conductive layer (copper) is shown, but it is clear that an intermediate layer may be provided to provide, for example, a rating of the feature. For example, an intermediate layer of an alloy may be provided. Other materials that may be included as the intermediate layer may include carbon and / or graphite materials capable of absorbing lithium and releasing absorption.

Laminate  Another treatment

Can be used as an electrode in a battery because it has formed a laminate of at least one layer comprising an electrically conductive layer and at least one active layer; Or may be further processed before use in a battery. For example, the laminate may be processed by one or more of the following treatments, but not necessarily in that order:

The laminate is cut to size;

The surface structure is applied as the active layer;

The active layer is chemically treated;

The laminate is heat treated;

The additional layer is applied using the same treatment as the dissimilar element or alloy to improve certain properties of the active layer, for example to reduce electrical impedance and to reduce mechanical damage in circulation;

The additional layer is applied by selective treatment to improve the specific characteristics of the active layer, for example by applying a carbon layer applied by chemical vapor deposition (CVD) to reduce the electrical impedance, Reduce mechanical damage;

· Physical or chemical treatments with lithium-containing materials (eg, SLMP® stabilized lithium metal powder from FMC lithium) can be made to increase the battery's first cycle efficiency from a negative electrode.

The surface structure is provided to provide stress relieving properties to the layer thereby accommodating the expansion of the active layer. For example, the active layer can be divided into ridges or islands so that the electrolyte can be accommodated in the gap therebetween or filled with other materials. Suitable treatments are disclosed in WO 2004/042851 and other treatments may be used.

The chemical treatment includes incorporating a doping material or other material into the active layer. The heat treatment includes an annealing step to relieve the stress generated in the production.

Other comments

The above description is an example of the invention, and the present invention is not limited to this example. The present invention includes all of these various features or any combination of the above and / or below disclosed embodiments. All combinations of features disclosed herein are considered to be part of the present invention and no limitations are intended with respect to combinable features.

The contents of the specification are hereby incorporated by reference in their entirety. In addition, when an amount, concentration, or other value or parameter is provided in a range, a preferred range, or an upper limit and a lower limit, it is formed into an upper limit or a desirable value or a lower limit or a desirable value regardless of whether the range is separately disclosed Quot; is intended to be &lt; / RTI &gt; When a numerical range is specified, it is not otherwise described, and such a range includes an end point and includes all integers and decimal places within the range. The scope of the present invention is not limited to the specific values recited when defining the ranges.

It will be apparent to those skilled in the art in light of the teachings of this invention that various alternative embodiments of the invention are possible. The description of the invention is to be considered as illustrative only.

Claims (43)

A method of manufacturing an article comprising one or more adherent coatings on a flexible substrate, the method comprising forming an ion beam and bombarding one or more flexible substrates with ions from the ion beam, So as to form said adhesion coating on a flexible substrate on which a beam is generated:
a) a first chamber for receiving one or more steam generators capable of forming steam in the state of one or more condensed materials;
b) a second chamber adjacent to the first chamber containing one or more plasma generators; End channel having at least one hollow cathode (anode) extending therethrough, said channel having at least one channel wall and a length extending from one end of the channel to the other end of the channel, And may form a plasma in one or more of such spaces;
c) one or more holes are disposed between the first chamber and the second chamber such that steam generated in the first chamber enters the second chamber, wherein the one or more steam generators and the one or more plasma generators are operatively associated with one or more vapors Wherein the vapor generated in the first chamber by the generator is arranged to cross at least one space through a plasma created in the second chamber by the at least one plasma generator. Gt; 2. The method of claim 1, wherein the steam generator is capable of generating vapor formation from a condensed state source of one or more materials. 3. The system of claim 2, wherein the steam generator comprises at least one electron beam generator operable to direct an electron beam to a condensed state source of the at least one substance. Method of manufacturing an article. 4. The apparatus of claim 3, wherein the at least one electron beam generator is operable to magnetically deflect electrons from the electron beam generator to a condensed state source of the at least one material. Method of manufacturing an article. 5. A flexible substrate according to any one of claims 1 to 4, characterized in that the at least one plasma generator further comprises at least one housing electrically isolated from and separated from one or more cathodes (anodes) RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; 6. A method according to any one of claims 1 to 5, further comprising a source for a magnetic field configured such that the at least one plasma generator is positioned parallel to one or more channel walls in a substantial portion of the channel length A method of making an article comprising at least one adhesion coating. 7. The method of claim 6, wherein the source of the magnetic field comprises at least one first magnet located proximate to the steam generator and at least one second magnet located further away from the steam generator. &Lt; / RTI &gt; 8. The method of claim 7, wherein the source for the magnetic field is comprised of an electrical magnet. A method according to any one of claims 6 to 8, wherein the magnetic shield is disposed between the vacuum generator and the plasma generator. The article of any one of claims 1 to 9, wherein the substrate is a coated substrate having a surface coating, wherein the adhesion coating forms the surface coating, characterized in that the article comprises at least one adherent coating on a flexible substrate Gt; A method according to any one of claims 1 to 10, wherein the layers are applied to the adhesive coating by the method. An apparatus for producing by vapor deposition an article comprising at least one adherent coating on a flexible substrate, the apparatus comprising:
a) at least one ion beam generator,
i) a first chamber for receiving one or more steam generators capable of forming steam in the state of one or more condensed materials;
ii) a second chamber adjacent to the first chamber receiving one or more plasma generators; End channel having one or more cathodes (anodes) extending therethrough, the channel having one or more channel walls and having a length extending from one end of the channel to the other end of the channel to create one or more spaces And may form a plasma in one or more of such spaces;
iii) one or more apertures disposed between the first chamber and the second chamber such that steam generated in the first chamber enters the second chamber, wherein the one or more steam generators and the one or more plasma generators are in operation one Wherein the steam generated by the at least one steam generator is arranged to traverse at least one space through a plasma created by the at least one plasma generator;
b) at least one gas supply operable to supply a gas for conversion into a plasma in the at least one ion beam generator, and
c) at least one substrate receiving area for receiving at least one substrate and for allowing passage of the substrate across the substrate receiving area, at least one substrate receiving area to be bombarded by ions from the at least one ion beam generator, Wherein the at least one substrate receiving area comprises at least one substrate receiving area for allowing at least one substrate to pass through when used in a chuck. &Lt; RTI ID = 0.0 &gt; 18. &lt; / RTI &gt; 13. The apparatus of claim 12, wherein the substrate receiving region comprises a substrate mount that allows passage of the substrate across the support. 13. The apparatus of claim 12 or 13, further comprising a source operative to apply a bias to a substrate passing across the substrate receiving region. 15. The apparatus of claim 14, wherein the source is operable to apply radio frequency to a substrate through which the substrate passes. A device according to any one of claims 12 to 15, characterized in that a heater is provided for heating the substrate. An article according to any one of claims 12 to 16, characterized in that at least one vent is located between the plasma chamber and the substrate receiving area, allowing the gas to approach the substrate receiving area. Lt; / RTI &gt; 17. A method according to any one of claims 12 to 17, characterized in that it comprises a source operable to inject gas in at least one region of the steam generator to prevent reaction between the reactive gas and the condensed state source surface of the material &Lt; / RTI &gt; by vapor deposition. A device according to any one of claims 12 to 18, operable to provide a lower pressure in the first chamber than in the second chamber. The apparatus of any one of claims 12 to 19, comprising a shutter selectively operable to prevent the transfer of vapor from the first chamber to the second chamber. 21. Apparatus according to any one of claims 12 to 20, characterized in that at least one housing (crucibles) is provided to receive the at least one condensed state source of material. 22. A method according to any one of claims 12 to 21, characterized in that the flexible substrate comprises a take-up spool for an article comprising a feed spool and at least one adhesion coating on the flexible substrate &Lt; / RTI &gt; by vapor deposition. An article comprising at least one adherent coating on a flexible substrate made by the method of any one of claims 1-11. 24. The article of claim 23, comprising a layer comprising AlN and having a thermal conductivity in excess of 210 W / mK. An electronic component mounted on an article according to claim 23 or 24; Optical-electronic components; Electronic-acoustic components; MEMS components; Or a spintronic component. A laminate for use as an electrode for a battery comprising: an electrically conductive layer operable as a current collector; and at least one solid state operative to absorb and remove charge transport elements during battery operation A laminate comprising at least one layer comprising at least one active layer, wherein the at least one active layer is an adhesion layer formed by vapor deposition. 27. The laminate of claim 26, wherein the at least one solid state serves to absorb lithium and remove it from the absorbent as a charge transport element. 28. The laminate of claim 27, wherein the at least one solid state comprises at least one element, an alloy, and an article, wherein they can form an alloy or compound with lithium. 29. The method of claim 28, wherein at least one solid state is selected from the group consisting of B, Mg, Al, Si, Zn, Ga, Ge, As, Se, Pd, Ag, Cd, In, Sn, Sb, Te, Pt, Au, Hg, Tl, Pb and Bi. 30. The laminate of claim 29, wherein the at least one solid state comprises an alloy of one or more of the elements and one or more other alloying elements. 31. The method of claim 30, wherein the at least one solid state comprises at least one element selected from the group consisting of Si, Sn, Sb, Ge, and Al and at least one element selected from the group consisting of B, Mg, Zn, Ga, As, Se, Pd, Ag, Te, Pt, Au, Hg, Tl, Pb, Bi, and the like. 31. The method of claim 30, wherein the at least one solid state comprises at least one element selected from the group consisting of Si, Sn, Sb, Ge, and Al and at least one element selected from the group consisting of B, Cr, Nb, Cu, Zr, Ag, Ni, Wherein the at least one element comprises at least one element selected from the group consisting of Mn, Sb, Zn, Ca, Mg, V, Ti, In, Al and Ge. 31. The laminate of claim 30, wherein the one or more other alloy elements comprise one or more elements that form part of an electrically conductive layer. 34. The laminate of claim 33, wherein the electrically conductive layer comprises copper and one or more solid state comprises alloy Cu6Sn5. 29. A laminate according to any one of claims 26 to 29, characterized in that at least one solid state comprises an oxide. The laminate according to any one of claims 26 to 35, wherein the active layer is discontinuous. 36. A laminate according to any one of claims 26 to 36, wherein the electrically conductive layer is capable of absorbing and removing the charge transport element during operation of the battery. 27. A laminate according to any one of claims 26 to 27, wherein the electrically conductive layer comprises a first electrically conductive layer and a laminate of one or more second electrically conductive layers. 39. The laminate of claim 38, wherein the at least one first electrically conductive layer and the at least one second electrically conductive layer can absorb and remove the charge transport element during operation of the battery. A method of forming a laminate according to any one of claims 26 to 39,
Forming an ion beam comprising at least one element capable of forming an alloy or compound with an element used as a charge transport element in a battery; And
Bombarding one or more electrically conductive substrates with ions from an ion beam,
At least one active layer and a laminate of said electrically conductive layer. 41. A method according to claim 40, characterized in that the device as claimed in the preceding claim or as claimed in WO2013 / 045596 is used. An electrode formed from a laminate as claimed in any one of claims 26 to 39. 42. A battery comprising an electrode as claimed in claim 42.

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