TW201435152A - Forming a transparent metal oxide layer on a conductive surface of a dielectric substrate - Google Patents

Abstract

A method and apparatus of forming a transparent metal oxide layer on a conductive surface of a dielectric substrate involves exposing first and second conductive surface portions of the conductive surface of the dielectric substrate to first and second electrolytes respectively to form first and second electrochemical cells in which the first conductive surface is part of the first electrochemical cell and the second conductive surface is part of the second electrochemical cell and wherein the electrochemical cells are electrically connected together by the conductive surface of the dielectric substrate. An electric potential applied across first and second counter electrodes in the first and second cells respectively drives an electric current through the first and second electrolytes and causes metal ions and oxygen in the second electrolyte to form the transparent metal oxide layer on the second conductive surface portion when a current is passed through the first and second electrolytes. The transparent metal oxide layer may be made non-conductive or conductive or even semi-conductive through the absence or inclusion of dopant in the second electrolyte. A conductive surface of a dielectric substrate of any length can be uniformly plated with a transparent metal oxide layer by moving the dielectric substrate relative to the first and second electrolytes while exposing the first and second surface portions to the first and second electrolytes respectively.

Description

Technique for forming a transparent metal oxide layer on a conductive substrate conductive surface Field of invention

The present invention is generally directed to forming a transparent metal oxide layer on a conductive surface of a dielectric substrate material (e.g., glass, ceramic or polymeric material). The transparent metal oxide layer can be electrically conductive, semi-conductive or non-conductive.

Background of the invention

The materials used to form the conductive coating generally fall into the following four categories: metals, metal oxides, conductive polymers, and nanomaterials. Metal coatings have the highest electrical conductivity, especially in the form of nanomaterials, although, for example, only ultra-thin continuous layers of about 5 to 10 nanometers thick can be considered transparent. The conductivity of metal oxides is generally orders of magnitude smaller than metal but provides better transparency. Conductive plastics are also much less conductive than metals but provide greater flexibility and sufficient transparency at lower cost. Nanomaterial coatings contain metals and metal oxides and are still in the laboratory stage of research and development. Current industrial applications require a transparent metal oxide layer to provide a transparent conductor for an electronic device, such as a flat panel display (FPD).

The transparent conductive oxide (TCO) is a metal-doped oxide film having a polycrystalline or microcrystalline or amorphous microstructure. These materials provide a transmittance of more than 80% for incident light in the visible spectrum and a resistivity of about 10 ^-3 to 10 ^-4 ohm.cm. A combination of two TCO layers each having a thickness of about 30-50 nm separated by an intermediate metal layer having a thickness of about 10-20 nm provides a composite structure in which the resistivity is reduced by a factor of ten and the light transmittance is increased by 95%. Recently, the industrial application of TCO has been greatly expanded. Rigid LCDs and other FPDs are the largest market for TCO coatings, but there are also many new market applications that utilize TCO coatings, including touch screen displays, flexible displays, transparent displays, organic light-emitting diode (OLED) displays, and wisdom. TCO coatings are also used for window and solid state lighting. While all of these techniques use TCO coatings to enable product functionality, the technical requirements of new applications for TCOs are often different from the typical technical requirements of conventional LCD displays.

Historically, the TCO market has been dominated by the demand for indium tin oxide (ITO). At the same time, sputtering has become a major deposition technique for TCO, especially ITO coatings. Although sputtered ITO has proven to meet industrial needs so far, both sputtering and ITO have many important drawbacks that are becoming more apparent.

One of the disadvantages is the manufacturing cost. Indium is a rare and expensive material and sputtering typically results in only about 30% of the indium and the remaining 70% is deposited on the walls of the sputtering chamber. In addition, prolonged downtime is often associated with vacuum-based sputtering and this is why the ITO TCO process has a high total cost. The operation and maintenance of vacuum devices, such as magnetron sputtering, is complicated. As a result, production lines using such devices typically require skilled workers and engineers to ensure stable line operations. In addition, magnetron sputtering requires ion impact to pretreat the substrate surface to provide a sputtered material. Adhesive. Finally, high temperatures are often associated with sputtering processes or post-annealing processes and this greatly limits the application of ITO coatings to substrates that can withstand high temperatures. As a result, the use of ITO-based TCO coatings on temperature sensitive substrates (eg, plastics) is challenging.

Another problem is that there is currently no viable alternative to ITO coatings that provide electrical and optical properties of ITO coatings, nor does the number require greater conductivity and optical transparency in growing market applications.

At this point, the end result is that for many existing market applications, the new ITO deposition process, which can replace the capital-intensive and wasteful material sputtering and have lower cost, has broad market opportunities. There is also a market for new "indium-free" TCO coating processes that offer lower cost and better performance ITO alternatives in the medium to long term. For this reason, new TCO materials, such as doped binary compounds (for example, aluminum-doped zinc oxide (AZO), indium-doped zinc oxide, antimony-doped zinc oxide, and cadmium-doped zinc oxide), are used in several laboratories. It has been tested and proposed as a substitute.

Alternative TCO deposition methods recently explored by industry and research groups include wet processing methods such as electrochemical methods. Electrochemical methods are based on current driven deposition of metals or metal oxides primarily on the surface of a substrate having a sufficient bulk conductivity. However, such methods are used to coat dielectric substrates (eg, glass, ceramics, and polymers) used in the manufacture of consumer products with theoretical limitations. Conductive surfaces are required to facilitate electrochemical processes for use on dielectric materials.

A thin layer of conductive metal oxide (for example, zinc oxide FznO, AZO or ITO doped with FZnO fluoride) can be deposited on glass by various deposition methods. Other dielectric substrates include, for example, metal organic chemical vapor deposition (MOCVD), metal organic molecular beam deposition (MOMBD), and sputtering, giving them potential for electrochemical processes.

U.S. Patent No. 5,316,697 issued to Palmer et al., entitled "CONDUCTIVE, PARTICULATE, FLUORINE-DOPED ZINC OXIDE" describes a process for the production of conductive, granular, fluorine-doped zinc oxide products by chemical vapor deposition. The method involves reacting a gas phase reactant in a gas phase oxidation system at a temperature sufficient to form a conductive, particulate, fluorine-doped zinc oxide product. The method uses a gas phase reactant comprising an elemental zinc vapor, at least one fluorine source, and at least one water source.

Glass sheets and polyester fiber films coated with conductive metal oxides are commercially available, for example, from Zhuhai Kaivo Electronic Components Co. Limited, No. 110, Jade Garden Road, Zhuhai, Guangdong, China.

Another possibility for making a conductive layer on the surface of a dielectric substrate involves an electroless deposition technique capable of fabricating a conductive surface on a non-conductive substrate, also known as autocatalytic plating. This is a non-galvanic plating method involving several sequential electrochemical reactions at the interface between the aqueous electrolyte and the surface of the non-conductive substrate, which occur without the use of external electrical power. For example, U.S. Patent No. 6,464,762 B1 to Ara, et al., entitled "Aqueous solution for the formation of indium oxide film by electroless deposition"; U.S. Patent No. 6,387,542 B1 to "Kelvin et al." "ELECTROLESS SILVER PLATING"; awarded to Kim US Patent No. 6,806,189 B2, et al., "Method of silver (Ag) electroless plating on ITO "Silver alloy plating bath and method of forming a silver alloy film by means of the same"; and Japanese Patent No. JP59143059 to ITSUPEI et al., "Electroless plating", issued to Igarashi et al. "Electroless plating for plastic", Japanese Patent No. JP11152578A, entitled "ELECTROLESS INDIUM OXIDE PLATING AQUEOUS SOLUTION AND ELECTROLESS PLATING METHOD"; and Japanese Patent No. JP 2057336 issued to YOSHIHIRO.

Unfortunately, the quality of the conductive layer made on the dielectric substrate by the above method is insufficient for consumer electronic products because the layer made by electroless deposition using CVD and sputtering techniques has low conductivity and thickness uniformity. Low, and low light transmittance. This has led to consideration of the use of pre-coated surfaces on dielectric substrates prior to the formation of transparent conductive metal oxide layers by electrochemical processes.

Several research institutes have demonstrated the possibility of forming cadmium-doped and antimony-doped zinc oxide on conductive surfaces pre-formed on glass substrates, but these results are only demonstrated with pre-samples and are made in conventional electrochemical chambers. Cheng, this is impractical for mass production industrial processes.

PCT Patent Application No. CA2011/001013 to "Electroplating Metal Oxides on Flat Conductive Surfaces" to Rubin et al. describes a method and apparatus for electrochemically forming an oxide layer on a flat conductive surface of a semiconductor element and photovoltaic (PV). On the battery. The method involves flattening a conductive surface of a working electrode and a counter electrode carrying a flat conductive surface They are relatively parallel. A volume of the chemical-containing organic electrolyte solution for forming an oxide layer on the flat conductive surface of the working electrode is configured to irrigate and occupy a space defined between the flat conductive surface of the working electrode and the opposite electrode. In the organic electrolyte solution, the current flows substantially only between the flat conductive surface and the working electrode in the opposite electrode only between the flat conductive surfaces for a period of time and in an amount sufficient to cause the chemical to form an oxide layer on the working electrode. The flat conductive surface. The device set is specifically designed such that the working and opposing electrodes can receive power on the back to protect their power input terminals from direct contact with electrolytes that could damage them. Therefore, the use of this device is very suitable for substrates having a volume conductivity and opposing electrodes but the device is not suitable for forming a metal oxide layer on a dielectric material even if their surfaces are previously coated with a conductive layer.

Therefore, it is still a challenge to form a highly uniform conductive metal oxide layer having high conductivity and high transparency while protecting the electrical terminals of the electrochemical device from interaction with the electrolyte over a large substrate area.

Summary of invention

According to one aspect of the invention, a method of forming a transparent metal oxide layer on a conductive substrate conductive surface is provided. The method includes: exposing each of the first and second conductive surface portions of the conductive surface of the dielectric substrate to the first and second electrolytes, and forming the first conductive contact with the first electrolyte The first electrochemical cell of the surface portion and the first electrode in contact with the first electrolyte and spaced apart from the first conductive surface portion. And the method further comprises: forming a second electrolyte a second electrochemical cell formed by the second conductive surface portion in contact with the second electrode in contact with the second electrolyte and partially separated from the second conductive surface. The first and second electrochemical cells are electrically connected together in series by the conductive surface. The first electrolyte has a first chemical that promotes current conduction through the first electrolyte such that the first electrode or the first conductive surface portion is less prone to significant electrochemical reactions. The second electrolyte has a second chemical that promotes current conduction through the second electrolyte, the second chemical comprising a non-aqueous solvent having a metal ion concentration at least sufficient to promote formation of the transparent metal oxide layer to a desired thickness An ion, and an oxygen source adapted to promote formation of the transparent metal oxide surface of the second conductive surface portion. And the method further includes: applying an electric current between the first electrode and the second electrode such that the second electrode has a positive polarity with respect to the first electrode to cause a current between the second electrode and the first electrode Flowing through the second electrolyte, the second conductive surface portion, the first conductive surface portion, and the first electrolyte in series. The second electrode has a positive potential sufficiently greater than the second conductive surface portion to cause an electrochemical reaction at the second conductive surface portion to form the transparent metal oxide layer on the second conductive surface portion on.

The nonaqueous solvent may be a protic or aprotic solvent.

The method can include: releasing a metal ion capable of forming the transparent metal oxide layer optically transparent in a visible region of the electromagnetic spectrum from a salt soluble in the non-aqueous solvent.

The method can include causing the second electrolyte to comprise a dopant electrochemically intercalated into the transparent metal oxide layer to produce a conductive transparent Metal oxide layer.

The method can include introducing a chemical additive to at least one of the first and second electrolytes.

The method can include calculating a Coulomb number of the charge in the current, and stopping applying the potential when the charge coulomb number meets a charge number criterion associated with a desired thickness of the transparent metal oxide layer.

The method can include interrupting the current, replacing the second electrolyte, and reestablishing the current when the metal ion concentration in the second electrolyte conforms to a metal ion concentration criterion.

The method can include, when the current is flowing, moving the substrate relative to the first and second electrolytes from the first electrolyte to the second electrolyte to cause the transparent metal oxide layer to The longitudinal direction of the conductive surface of the substrate is formed.

The step of forming the first and second electrochemical cells can include storing the first electrolyte in a first open-faced container and storing the second electrolyte in a second kneading container.

The method may include defining the first and second kneading containers with an inlet wall, an inner wall, an outlet wall, a plurality of first end wall portions, and a first bottom wall portion, thereby defining the first crucible a surface container between the inlet wall, the inner wall, the first end wall portion and the first bottom wall portion, and thereby defining the second kneading container on the inner wall, the outlet wall, and the plurality of Between the two end wall portions and the second bottom wall portion.

The method can include extending the first electrode through the inlet wall, a first end wall portion, or the first portion at a first position spaced parallel to the substrate a bottom wall portion and the second electrode extending through the outlet wall, a second end wall portion or the second bottom wall portion at a second position spaced parallel to the substrate.

The method can include introducing the dielectric substrate having the conductive surface through an opening in the inlet wall, and extending the substrate over the first and second kneading containers such that the conducting The surface faces the first and second kneading containers. The first conductive surface portion is a portion of the conductive surface that extends over the first container, and the second conductive surface portion is the conductive surface that extends over the second kneading container A portion of the method, and the method may further comprise: causing a portion of the substrate to extend through an exit opening of the outlet wall of one of the second kneading containers.

The method can include causing the conductive opening against the dielectric substrate to seal the inlet opening and the outlet opening to prevent the first and second electrolytes from being exposed by the inlet and the outlet opening, respectively.

The method can include causing the conductive surface against the dielectric substrate to seal the inner wall to prevent the first and second electrolytes from being exchanged at the inner wall.

The method can include, when the current is flowing, moving the substrate relative to the first and second electrolytes from the first electrolyte to the second electrolyte to cause the transparent metal oxide layer to The longitudinal direction of the conductive surface of the substrate is formed.

The moving step can include moving the substrate while the first and second kneading containers remain stationary.

The method can include: causing the first and second kneading containers to be placed face down on the conductive surface of the dielectric substrate such that the substrate Extending the inlet wall, the inner wall, the outlet wall, and the first and second end wall portions such that the first and second conductive surfaces of the dielectric substrate face the first and the first Two-face container. The first conductive surface portion is a portion of the conductive surface that extends under the first kneading container, and the second conductive surface portion is the conductive surface of the second kneading container A further extension, and the method, further comprising: extending a portion of the conductive surface of the dielectric substrate below the exit wall of the second kneading container.

The method can include: storing the substrate with the conductive surface facing up in a container for storing an initial electrolyte, and placing the first and second kneading containers face down on the dielectric substrate The conductive surface of the material. This may include: substantially immersing the first and second kneading containers in the initial electrolyte and sealing the inlet wall, the outlet wall, the first and second end wall portions against the substrate to accommodate the initial A first volume of the electrolyte is in the first kneading container and a second volume containing the initial electrolyte is in the second kneading container.

The method can include causing the conductive surface against the dielectric substrate to seal the inner wall to prevent the first and second electrolytes from being exposed underneath the inner wall.

The method can include, when the current is flowing, moving the substrate relative to the first and second electrolytes from the first electrolyte to the second electrolyte to cause the transparent metal oxide layer to The longitudinal direction of the conductive surface of the substrate is formed. The moving step can include moving the first and second kneading containers while the substrate remains stationary.

In accordance with another aspect of the invention, a method of forming a transparent metal oxide layer on a first conductive surface of a first dielectric substrate is provided. The method includes: pressing a first conductive surface of the first dielectric substrate against a space-defining frame gasket of a defined space on a second conductive surface of the second dielectric substrate The frame defines a confined space between the first conductive surface and the second conductive surface. And the method further comprises: introducing an electrolyte into the sealed space through an opening in the frame gasket, the electrolyte having a chemical that promotes current conduction through the electrolyte, the chemical comprising a non-aqueous solvent, a metal ion The metal ion having a concentration at least sufficient to promote formation of the transparent metal oxide layer to a desired thickness, and an oxygen source adapted to promote formation of the surface of the transparent metal oxide of the second conductive surface. And the method further includes: applying an electric current between the first conductive surface and the second conductive surface such that the second conductive surface has a negative polarity to the first conductive surface to cause a current in the first conductivity A flow is passed between the surface and the second conductive surface through the electrolyte to cause an electrochemical reaction to occur at the first conductive surface to form the transparent metal oxide layer on the first conductive surface.

The nonaqueous solvent may be a protic or aprotic solvent.

The method can include: releasing a metal ion capable of forming the transparent metal oxide layer optically transparent in a visible region of the electromagnetic spectrum from a salt soluble in the non-aqueous solvent.

The method can include causing the second electrolyte to comprise a dopant that can be electrochemically embedded in the transparent metal oxide layer to produce a conductive transparent metal oxide layer.

The method can include introducing a chemical additive into the electrolyte.

The method can include calculating a Coulomb number of the charge in the current, and stopping applying the potential when the charge coulomb number meets a charge coulomb number criterion associated with a desired thickness of the transparent metal oxide layer.

The method can include interrupting the current, replacing the electrolyte, and reestablishing the current when the metal ion concentration in the electrolyte conforms to a metal ion concentration criterion.

The pressing step may include: sufficiently pressing to compress the frame spacer for the defined space to sufficiently seal the sealed space to prevent the electrolyte from being exposed by the sealed space.

The step of applying a potential may include: respectively fixing the first and second conductive clamps on the first and second opposite edges of the first substrate to be at the opposite edge of the first substrate and the first conductivity Surface electrical contact, and respective fixed third and fourth conductive clamps on the third and fourth edges of the dielectric substrate to electrically contact the second conductive surface of the dielectric substrate, and to cause The first and second clamps are coupled to the positive terminal of a current source and the third and fourth clamps are coupled to the negative terminal of the current source.

In accordance with another aspect of the invention, an apparatus for forming a transparent metal oxide layer on a conductive surface of a dielectric substrate is provided. The device includes a member for storing a first electrolyte and a first electrode in contact with the first electrolyte, and a member for storing the second electrolyte and the second electrode in contact with the second electrolyte. The device further includes a member for simultaneously exposing each of the first and second conductive surface portions of the conductive surface of the dielectric substrate to the first and second electrolytes such that the first and the first The second conductive surface portions are each spaced apart from the first and second electrodes to form first and second electrochemical cells, respectively, and thereby the first and second electrochemical cells are used with the dielectric substrate The conductive surfaces are electrically connected together in series. The first electrolyte has a first chemical that promotes current conduction through the first electrolyte such that the first electrode or the first conductive surface portion is less prone to significant electrochemical reactions. The second electrolyte has a second chemical that promotes current conduction through the second electrolyte, the second chemical comprising a non-aqueous solvent having a metal ion concentration at least sufficient to promote formation of the transparent metal oxide layer to a desired thickness An ion, and an oxygen source adapted to promote formation of the transparent metal oxide layer on the second conductive surface portion. The device further includes a member for applying an electric current between the first electrode and the second electrode such that the second electrode has a positive polarity with respect to the first electrode to cause a current at the second electrode and the first electrode Flowing through the second electrolyte, the second conductive surface portion, the first conductive surface portion, and the first electrolyte in series. The second electrode has a positive potential sufficiently greater than the second conductive surface portion to cause an electrochemical reaction at the second conductive surface portion to form the transparent metal oxide layer on the second conductive surface portion on.

The nonaqueous solvent may be a protic or aprotic solvent.

The apparatus can comprise a metal ion that is soluble in the transparent metal oxide layer that is optically transparent in the visible region of the electromagnetic spectrum by a salt that is soluble in the non-aqueous solvent.

The device can include causing the second electrolyte to comprise a dopant that can be electrochemically embedded in the transparent metal oxide layer to produce a conductive transparent Metal oxide layer.

The apparatus can include a component for calculating a Coulomb number of the charge in the current, and a component for communicating with the member for calculating the Coulomb number for satisfying the charge coulomb number indicated by the member for calculating the Coulomb number The application of the potential is stopped when the desired thickness of the transparent metal oxide layer is associated with one of the Coulomb number criteria.

The device may comprise a means for interrupting the current when the metal ion concentration in the second electrolyte conforms to a metal ion concentration criterion, a means for replacing the second electrolyte, and for replacing the second electrolyte After rebuilding a component of the current.

The device may include a member for causing the substrate to move from the first electrolyte to the second electrolyte relative to the first and second electrolytes while the current is flowing to cause the transparent metal to oxidize The layer is formed along the longitudinal direction of the conductive surface of the substrate.

The member for storing the first electrolyte and the first electrode may comprise a first kneading container, and the member for storing the second electrolyte and the second electrode may comprise a second kneading container.

The first kneading container may include an inlet wall and an inner wall, a pair of first end walls, and a first bottom wall portion, and the second kneading container may include the inner wall and an outlet wall, a pair of The second end wall and the second bottom wall portion, the first and second kneading containers have first and second end wall portions.

The first electrode may extend through the inlet wall at a first position spaced parallel to the substrate, at least one of the first end wall portion or the first bottom wall portion, and the second electrode The conductivity table with the dielectric substrate The second position parallel to the face may extend through the outlet wall, at least one of the second end wall portion or the second bottom wall portion.

The member for simultaneously exposing the first and second surface portions of the substrate conductive surface may include an inlet opening in the inlet wall and an outlet opening in the outlet wall for receiving And positioning the dielectric substrate such that the dielectric substrate extends over the first and second kneading containers such that the first conductive surface portion faces the first kneading container and the second conductivity is made The surface portion faces the second kneading container.

The device can include an inlet and an outlet seal, the inlet and the outlet seal being operatively configured to seal the inlet opening and the outlet opening against the conductive surface of the dielectric substrate to prevent The first and the second electrolyte are each exposed by the inlet and the outlet opening.

The device can include an inner wall seal operatively configured to seal the inner wall against the conductive surface of the dielectric substrate to prevent the first and second electrolytes from The inner wall is exchanged.

The device may include a member for causing the substrate to move from the first electrolyte to the second electrolyte relative to the first and second electrolytes while the current is flowing to cause the transparent metal to oxidize The layer is formed along the longitudinal direction of the conductive surface of the substrate.

The member for movement may include a member for moving the substrate and a member for holding the first and second kneading containers stationary while the substrate is moving.

The device may further include: a member for placing the first and second kneading containers on the conductive surface of the dielectric substrate face down; The substrate extends over the inlet wall, the inner wall, the outlet wall, and the first pair and the second pair of end walls such that the first and second conductive surfaces of the dielectric substrate face the The first and the second kneading container.

The apparatus can include a member for storing a volume of an initial electrolyte for depositing a member of the dielectric substrate in the initial electrolyte with the conductive surface facing up, and for placing face down The member of the first and second kneading containers on the conductive surface of the dielectric substrate can comprise a member for substantially immersing the first and second kneading containers into the initial electrolyte. The device may further comprise a member for sealing the inlet wall, the outlet wall and the first and second end wall portions against the substrate to accommodate a first volume of the initial electrolyte in the first kneading container And a second volume containing the initial electrolyte in the second kneading container.

The device can include a member for sealing the inner wall against the conductive surface of the dielectric substrate to prevent the first and second electrolytes from being exposed at the inner wall.

The device may include a member for causing the substrate to move from the first electrolyte to the second electrolyte relative to the first and second electrolytes while the current is flowing to cause the transparent metal to oxidize The layer is formed along the longitudinal direction of the conductive surface of the substrate.

The member for moving may include a member for moving the first and second kneading containers, and for holding the substrate stationary while the first and second kneading containers are moving A component.

According to another aspect of the present invention, there is provided a device for forming a transparent metal oxide layer on a first conductive surface of a first dielectric substrate Set. The device includes a frame spacer for defining a space on the conductive surface of the dielectric substrate. The gasket has an inner wall defining a space bounded by the inner wall and a portion of the conductive surface of the dielectric substrate. The device further includes a member for pressing the second conductive surface of the second dielectric substrate against the frame spacer for the defined space to make the space a closed space, and in the frame gasket An opening is used to introduce an electrolyte having a chemical that conducts current through the electrolyte in the enclosed space. The chemical comprises a non-aqueous solvent, a metal ion, and an oxygen source adapted to promote formation of the transparent metal oxide layer on the conductive surface of the first dielectric substrate. The device further includes a member for applying an electric current between the second conductive surface of the second dielectric substrate and the first conductive surface of the first substrate such that the first substrate a conductive surface having a negative polarity to the second conductive surface of the second dielectric substrate such that a current flows between the second conductive surface and the first conductive surface to pass through the electrolyte to cause The first conductive surface undergoes an electrochemical reaction to form the transparent metal oxide layer on the first conductive surface.

The nonaqueous solvent may be a protic or aprotic solvent.

The apparatus can comprise a metal ion that is soluble in the transparent metal oxide layer that is optically transparent in the visible region of the electromagnetic spectrum by a salt that is soluble in the non-aqueous solvent.

The apparatus can include causing the second electrolyte to comprise a dopant that can be electrochemically embedded in the transparent metal oxide layer to produce a conductive transparent metal oxide layer.

The device can include a component for calculating the charge in the current a Coulomb number, and a component for communicating with the member for calculating the Coulomb number, is used to satisfy a coulomb number associated with the desired thickness of the transparent metal oxide layer in the component used to calculate the Coulomb number. The application of this potential is stopped when the number criterion is used.

The apparatus may include a member for interrupting the current when the metal ion concentration in the electrolyte conforms to the metal ion concentration criterion, a member for replacing the electrolyte, and a means for reestablishing the current after replacing the electrolyte member.

The member for pressing is operatively assembled to form a frame gasket that is sufficiently compressible to compress the defined space to sufficiently seal the enclosed space to prevent the electrolyte from being exposed from the enclosed space.

The member for applying a potential may include a first one electrically contacting the first conductive coating on opposite sides of the first substrate on the first and second opposite edges of the first substrate And a second conductive clamp and third and fourth conductivity in electrical contact with the second conductive surface on opposite sides of the dielectric substrate on the third and fourth opposite edges of the dielectric substrate clamp. The first and second clamps are operatively configured to be coupled to a negative end of a current source, and the third and fourth clamps are operatively assembled to be connectable to the current source Positive end.

Other aspects and features of the present invention will become apparent to those skilled in the <RTIgt;

10‧‧‧ device

12, 18, 24, 26‧‧‧ components

14‧‧‧First electrolyte

16‧‧‧First electrode

20‧‧‧Second electrolyte

22‧‧‧second electrode

28, 30‧‧‧ First and second conductive surface parts

32‧‧‧ Conductive surface

34‧‧‧Dielectric substrate

36, 38‧‧‧ First and second electrochemical cells

50, 52‧‧‧ first and second kneading containers

53‧‧‧ Subject

54‧‧‧ entrance wall

56‧‧‧ inner wall

58‧‧‧ first pair of side walls

59‧‧‧Second pair of side walls

60, 66‧‧‧ first and second bottom wall sections

62‧‧‧Exit wall

70‧‧‧Long entrance opening

72, 74‧‧‧Upper and lower wall

76,78‧‧‧First upper and lower elastic seals

80‧‧‧ dielectric substrate

82‧‧‧ Conductive surface

84‧‧‧End

86‧‧‧ first surface

88‧‧‧ Non-conducting surface

90‧‧‧ outer edge

92‧‧‧First Conductive Clamp

94‧‧‧Contacts

96‧‧‧C-shaped channel

98, 100‧‧‧ first and second relative feet

102‧‧‧ screws

104‧‧‧Wire

106‧‧‧negative

107‧‧‧current source

108‧‧‧Power supply

109‧‧‧ Current shunt

110‧‧‧Long opening

111‧‧‧ Processor Circuit

112, 114‧‧‧Upper and lower wall

113‧‧‧ Relay

116, 118‧‧‧Second upper and lower elastic seals

120‧‧‧Substrate

122‧‧‧ Non-conductive lower surface

124‧‧‧Non-conducting upper surface

126‧‧‧ end

128‧‧‧second surface

130‧‧‧Second conductive clamp

132‧‧‧Wire

134‧‧‧ Positive

150‧‧‧ entrance opening

152‧‧‧Export opening

154, 156‧‧‧ upper and lower entrance walls

158, 160‧‧‧ upper and lower inlet seals

162, 164‧‧‧Upper and lower walls

166, 168‧‧‧ upper and lower outlet seals

170‧‧‧ upper half

172‧‧‧Inner wall seals

180, 182, 184‧‧‧ elongated openings

186, 188, 190‧‧‧ heater elements

192, 194‧‧‧ Electrolyte introduction opening

196, 198‧‧‧ Electrolyte discharge opening

200, 202‧‧‧ entrance and exit slots

201‧‧‧ equivalent circuit

203‧‧‧First resistance

205‧‧‧second resistance

207‧‧‧ Third resistor

209‧‧‧fourth resistor

211‧‧‧ fifth resistor

213‧‧‧ sixth resistor

215, 217‧‧ interface

220‧‧‧First entrance winch

222‧‧‧Inlet pinch roller

224‧‧‧Export winch

226‧‧‧Export pinch roller

228‧‧‧ arrow

246‧‧‧ Conductive surface

248‧‧‧ dielectric substrate

250‧‧‧ system

252‧‧‧One roll of PET film

254‧‧‧ mandrel

256‧‧‧Counterclock direction

258‧‧‧Winning mandrel

300‧‧‧ device

302‧‧‧Deep disk container

303‧‧‧Injection opening

304, 306‧‧‧ first and second end walls

307‧‧‧Draining holes

308, 310‧‧‧ first and second side walls

312‧‧‧ bottom wall

314‧‧‧Long opening

316‧‧‧Initial electrolyte

318‧‧‧Substrate

320‧‧‧ Conductive surface

350‧‧‧ device

352, 354, 356‧ ‧ entrance, exit and inner wall

358‧‧‧ side wall

360‧‧‧ bottom wall

362, 364, 366‧‧‧ coplanar distal surface

368, 370, 372‧‧‧ elastic seals

380‧‧‧ first kneading container

381‧‧‧First volume

382‧‧‧Second kneading container

383‧‧‧second volume

390, 392‧‧‧ first and second electrodes

393, 394‧‧‧ long open holes

396, 398‧‧‧ elastic seals

400, 402‧‧‧ first and second openings

420‧‧‧ components

422, 424‧‧‧ first and second conductive surface parts

430‧‧‧ horizontally telescopic arm

432‧‧‧ Vertically extendable bracket

433‧‧‧ arrow

440‧‧‧Final second conductive surface part

442‧‧‧ final first surface part

500‧‧‧ device

502‧‧‧Electrochemical battery pack

503‧‧‧First electrode

504‧‧‧Compression assembly

505‧‧‧second electrode

506‧‧‧ Conductive surface

507‧‧‧Rectangular dielectric substrate

508, 510‧‧‧ first and second edges

512, 514‧‧ ‧ clamp

513, 515‧‧‧ wires

516‧‧‧Defined space gasket for space

517‧‧‧flat surface

518‧‧‧ side

520‧‧‧Rectangular opening

522‧‧‧ inner wall

524‧‧‧ Space

526‧‧‧Parts

528‧‧‧ Frame Department

530, 532‧‧‧ first and second openings

534, 536‧‧ first and second catheters

550‧‧‧Second substrate

552‧‧‧Second conductive surface

554, 556‧‧‧ third and fourth clamps

555, 557‧‧‧ wires

558, 560‧‧‧ first and second edges

600, 602‧‧‧ first and second steel plates

604‧‧‧First outwardly extending side

606, 608‧‧‧ first and second outwardly extending sides

610, 612‧‧‧ first opening

614, 616‧‧‧ bolts

618‧‧‧Threading Department

620‧‧‧Smooth Department

622‧‧‧ head

1 is a perspective view of a device in accordance with a first embodiment of the present invention; Figure 2 is a cross-sectional/perspective view of the apparatus of Figure 1, wherein the cross-sectional view is taken along line 11-11 of Figure 1; Figure 3 is a schematic representation of the circuit formed by the apparatus of Figures 1 and 2; Figure 4 A system comprising the apparatus of Figures 1 and 2, and means for moving a substrate against the apparatus to cause formation of a transparent metal oxide layer on a long substrate, in accordance with a second embodiment of the present invention; BRIEF DESCRIPTION OF THE DRAWINGS A schematic view of a device according to a third embodiment of the present invention, wherein a polymeric dielectric substrate having a conductive surface is wound onto a reel and fed into the apparatus of Figures 1 and 2, and then through Figures 1 and 2 After processing the device, it is wound on a take-up reel; FIG. 6 shows a device according to a fourth embodiment of the present invention, which is a variant that uses a direction opposite to that of the device of FIGS. 1 and 2 and for the device to contain Figure 7 is a cross-sectional/fragment view of the apparatus of Figure 6, wherein the cross-section is depicted along line VII-VII of Figure 6; Figure 8 is a diagram of a fifth embodiment of the present invention A perspective/schematic diagram showing a device using only a single electrochemical cell; an expanded view of Figure 9. The electrochemical cell portion of the device of Figure 8 is illustrated.

Detailed description of the preferred embodiment

1 generally illustrates, by reference numeral 10, a device for forming a transparent metal oxide layer on a conductive surface 32 of a dielectric substrate 34 in accordance with a first embodiment of the present invention. In this embodiment, the dielectric substrate can be a glass or ceramic material having a thickness of from about 0.3 mm to about 4 mm or about 0.05 mil. The polymeric material having a thickness of from about 1 mm to about 1 mm, and the transparent conductive surface 32 may, for example, have a thickness between about 20 nm and about 1000 nm and a sheet resistance of from about 500 ohms per unit area to about 5 ohms per unit. A layer of fluorine-doped zinc oxide between the areas. The dielectric substrate 34 can be several meters long.

In this particular embodiment, the device includes a member generally designated by the numeral 12 for storing the first electrolyte 14 and the first electrode 16 in contact with the first electrolyte 14. Device 10 further includes a member generally indicated by reference numeral 18 for storing a second electrolyte 20 and a second electrode 22 in contact with the second electrolyte. Device 10 also includes components generally designated by reference numerals 24 and 26 for simultaneously exposing first and second conductive surface portions 28, 30 of conductive surface 32 of dielectric substrate 34 to first and second portions, respectively. Electrolytes 14, 20. First and second conductive surface portions 28, 30 are each spaced apart from first and second electrodes 16, 22 to form first and second electrochemical cells 36, 38, respectively, whereby first and second electrochemical cells 36, 38 are electrochemically joined together in series by the conductive surface 32 of the dielectric substrate 34.

The primary function of the first electrolyte 14 is to conduct current between the first conductive surface portion 28 and the first electrode 16. The chemical composition of the first electrode can be simple and, for example, can comprise only solvents and dissolved potassium chloride salts. With this simple chemical composition, there is no significant chemical reaction at the first electrode or first conductive surface portion that would significantly degrade both entities. The second electrolyte 20 has a more complex chemical composition. The chemical composition of the second electrolyte 20 is configured to promote conduction of current through the second electrode 22, the second conductive portion 30, and to promote electrochemical formation of the desired transparent metal oxide layer on the dielectric substrate 34. The second conductive surface portion 30 is on. second The chemical in the electrolyte 20 includes a non-aqueous solvent at a concentration at least sufficient to promote formation of the transparent metal oxide layer on the second conductive surface portion 30 to a desired thickness of metal ions, and to promote formation of the transparent metal oxide layer. An oxygen source 30 on the second conductive surface portion. The device 10 further includes means for applying a voltage between the first and second electrodes 16, 22 such that the second electrode 22 has a positive polarity with respect to the first electrode 16 to cause a current at the second electrode 22, the first electrode 16 The second electrolyte 20, the second conductive surface portion 30, the first conductive surface portion 28, and the first electrolyte 14 are flowed in series between them. This establishes a circuit in which the second electrode 22 has a positive potential sufficiently greater than that of the second conductive surface portion 30 to cause an electrochemical reaction at the second conductive surface portion 30 to form the transparent metal oxide layer. Two conductive surface portions 30.

Referring to FIG. 2, the member 12 for storing the first electrolyte 14 and the member 18 for storing the second electrolyte 20 are each composed of first and second kneading containers 50, 52. The first and second kneading containers 50, 52 have an inlet wall 54, an inner wall 56, an outlet wall 62, a first pair of side walls (only one of which is shown at 58 in Fig. 2), and a second pair of side walls (Fig. 2 The main body 53 of the first and second bottom wall portions 60, 66 is formed only by one of the 59 drawings. The inlet wall 54, the inner wall 56, the first pair of side walls (58) and the first bottom wall portion 60 define a first kneading container 50. The second kneading container 52 is defined by an inner wall 56, an outlet wall 62, a second pair of side walls (64), and a second bottom wall portion 66.

The body 53 can be made of anodized aluminum, Teflon, plexiglass or other materials that are chemically and mechanically stabilized by Teflon reflow. The length of the body 53 can be defined between the outer surfaces of the inlet and outlet walls 54, 62 And can be about 10 cm to about 200 cm long. The width of the body 53 can be defined on the outer surface of each pair of side walls 58, 59 and can be from about 10 cm to about 200 cm long. The width of the dielectric substrate 34 on which the transparent metal oxide layer is to be formed may determine the width. The height of the body 53 can be between 4 cm and about 50 cm. Of course, the heights define the depths of the first and second kneading containers 50, 52, respectively, and can be set within the above range to allow for the respective first and second electrodes and the first conductive surface portion 28 and the second conductivity. The surface portions 30 are suitably spaced and in view of the sufficient volume of the first and second electrolytes 14, 20 to provide a suitable chemical supply for forming the transparent metal oxide to the desired thickness. For example, the first and second kneading containers 50, 52 can be from about 3 cm to about 47 cm deep and from about 20 cm to about 190 cm wide, but can vary in length. For example, the first kneading container 50 can be from about 10 cm to about 50 cm in length, and the second kneading container 52 can be from about 2 cm to about 150 cm in length.

Referring again to FIG. 2, the first electrode 16 extends through the inlet wall 54 at a first position spaced parallel to the first conductive surface portion 28, and the second electrode 22 is spaced parallel to the second conductive surface portion 30. The open second position extends through the outlet wall 62. To facilitate this, the inlet wall 54 is provided with elongated inlet openings 70 having upper and lower wall portions 72, 74 that respectively secure the first upper and lower resilient seals 76, 78 thereon. The first upper and lower elastic seals 76, 78 may be made of a soft elastic rubber material such as Vitom ^(TM) available from the American company EI du Pont de Nemours and Company.

The first electrode 16 is a planar electrode comprising a dielectric substrate 80 (e.g., glass), for example, having a thickness of about 0.3 to 4 mm, and a conductive surface 82 disposed on a wide surface. The conductive surface 82 can be made of a chemically stable material, such as For example, fluorine-doped zinc oxide having a thickness of about 300 nm to about 1500 nm and a sheet resistance of about 20 Ω/sq to about 0.1 Ω/sq. This conductive layer can be formed on dielectric substrate 80 using, for example, CVD or sputtering techniques. The first electrode 16 is inserted through the inlet opening 70 such that the end 84 of the first electrode is adjacent the first surface 86 of the inner wall 56. A support (not shown) may be provided to position the end 84 such that the first electrode will be parallel to the first conductive surface portion 27. The first upper and lower elastic seals 76, 78 are pressed against the conductive surface 82 and the non-conductive surface 88 of the first electrode 16 to prevent the first electrolyte 14 from being exposed through the inlet opening 70. The first electrode 16 further has an outer edge 90 extending outside the first kneading container 50. The outer electrode 90 is fixed to the outer edge 90 by a contact member 94 and a C-shaped channel 96 having first and second opposing legs 98, 100. First conductive clamp 92. The contact member 94 is received between the first leg portion 98 and the conductive surface 82 of the first electrode 16 for contact therewith. Contact 94 is made of a sufficiently soft conductive metal, such as silver or indium, for example. A screw as shown at 102 is mounted to press the contact 94 against the conductive surface 82 to make good electrical contact therewith. The clamp 92 is connected to a wire 104 that is connected to the negative end 106 of the power supply 108.

Similarly, the outlet wall 62 is provided with elongated openings 110 having upper and lower wall portions 112, 114 that each secure the second upper and lower resilient seals 116, 118. The second electrode 22 is identical to the first electrode 16 and has a substrate 120 having a non-conductive lower surface 122 and a non-conductive upper surface 124. The second electrode 22 is inserted into the opening 110 until its end 126 abuts the second surface 128 of the inner wall 56. A support (not shown) may be provided to position the end 126 such that the second electrode will be parallel to the second conductive surface portion 30. The second upper and lower elastic seals 116, 118 are the same as those mentioned in the description of the first electrodes (76 and 78) and The conductive and non-conductive surfaces 124, 122 are abutted to seal the opening 110 to prevent the second electrolyte 20 from being exposed through the opening 110. The second electrode is provided with the same second conductive clamp 130 as the conductive clamp 92 for the first electrode 16 and the wire 132 is connected to the second conductive clamp 130 to connect it to the power supply 108 Positive end 134.

The first electrode 16 can be spaced apart from the first conductive surface portion 28 by between about 1 mm and about 50 mm. The second electrode 22 and the second conductive surface portion 30 can be separated by the same distance.

A member for simultaneously exposing each of the first and second conductive surface portions 28, 30 of the substrate 34 conductive surface 32 to the first and second electrolytes includes an inlet opening 150 at the inlet wall 54 and an outlet The outlet opening 152 of the wall 62 is adapted to receive and position the dielectric substrate 34 such that the dielectric substrate extends over the first and second kneading containers 50, 52 such that the first conductive surface portion 28 faces the first side The face container 50 and the second conductive surface portion 30 face the second kneading container 52. The inlet openings 150 have upper and lower inlet walls 154, 156 that are each attached to the upper and lower inlet seals 158, 160. The upper and lower inlet seals 158, 160 are identical to the elastomeric seals 76, 78. The upper inlet seal 58 is pressed against the uncoated surface of the dielectric substrate 34 while the lower inlet seal 160 is pressed against the conductive surface 32 of the substrate to seal the inlet opening to prevent the first electrolyte 14 from being opened by the inlet opening 150. Exposed.

Likewise, the outlet openings 152 have upper and lower walls 162, 164 that are each coupled to the same upper and lower outlet seals 166, 168 as the elastomeric seals 116, 118. The upper outlet seal 166 is pressed against the uncoated surface of the substrate 34 while the lower outlet seal 168 is pressed against the second conductive surface portion 30 of the dielectric substrate 34. The outlet opening 152 is sealed to prevent the second electrolyte 20 from being exposed by the outlet opening 152. The inlet and outlet openings 150, 152 are disposed in a common substrate plane that is parallel and spaced apart from the electrode plane in which the first and second electrodes 16, 22 are located. The substrate plane and electrode plane are configured such that the first and second electrolytes 14, 20 can each contact the entire first and second conductive surface portions 28, 30 of the conductive surface 32. In the illustrated embodiment, the inner wall 56 is disposed intermediate the inlet wall, the outlet walls 54, 62, and has an upper half 170 that is slightly below the plane of the substrate. Inner wall seal 172 is disposed on upper half 170 to contact conductive surface 32 of dielectric substrate 34. The thickness of the inner wall seal 172 is approximately the same as the thickness of the lower inlet seal 160. This can sufficiently prevent ion exchange between the first electrolyte 14 and the second electrolyte 20. If the thickness of the inner wall seal 172 is less than the thickness of the inlet seal 160, a space is formed between the conductive surface 32 of the substrate 34 and the inlet seal 172, resulting in a relationship between the first electrolyte 14 and the second electrolyte 20. Ion exchange path (not shown). The generation of an ion exchange path through the first and second electrolytes 14, 20 between the first and second electrodes 16, 22 may result in undesirable metal oxide plating on the first electrode 16.

As best seen in Figure 1, the inlet wall 54, inner wall 56 and outlet wall 62 each have elongated openings 180, 182 and 184 that receive heater elements 186, 188 and 190, respectively, for which heater elements 186, 188 and 190 are used. The first and second kneading vessels 50, 52 are heated and ultimately used to heat the first and second electrolytes 14, 20 to a temperature of between about 15 ° C and about 120 ° C. Referring again to Figure 2, in the illustrated embodiment, the first, second, and third elongate apertures 180, 182, and 184 are all disposed in a plane approximately midway between the substrate plane and the electrode plane.

Referring again to Figure 2, the first and second bottom wall portions 60, 66 have respective electrolyte introduction openings 192, 194 and respective electrolyte discharge openings 196, 198. The electrolyte introduction openings 192, 194 can be connected to respective conduits (not shown) for supplying the volumes of the first and second electrolytes 14, 20. The discharge openings 196, 198 can be connected to a common drain (not shown) or a recovery device for recovering and/or reusing the first and second electrolytes 14, 20.

Ideally, the first and second electrodes 16, 22 and the dielectric substrate 34 are placed in the position shown in Figure 2 prior to introduction of any electrolyte into the first or second kneading container 50 or 52. Once the first and second electrodes 16, 22 are in place, the volumes of the first and second electrolytes 14, 20 are dispensed through the electrolyte introduction openings 192, 194 into the first and second kneading vessels 50, 52 until the first electrolyte 14 contacts the first conductive surface portion 28 of the dielectric substrate 34 and until the second electrolyte 20 contacts the second conductive surface portion 30. For example, the inlet and outlet channels 200, 202 adjacent the inlet and outlet openings 150, 152 can be used to collect any electrolyte that is exposed through the seals at the inlet or outlet openings 150, 152.

The first and second electrolytes 14, 20 have chemicals that promote current conduction therethrough and may include at least methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerol, and tetrahydrofurfuryl alcohol. One of the protic non-aqueous solvents.

Alternatively, they may comprise at least one of N-Methylacetamide, dimethylformamide, acetonitrile, dimethyl hydrazine (DMSO), and propylene carbonate. A non-protic non-aqueous solvent.

As described above, the first electrolyte 14, for example, can be simple and contains only a nonaqueous solvent and at least one salt such as potassium chloride to account for conductivity.

At least the second electrolyte 20 has a chemical composition comprising a source of oxygen sufficient to allow formation of a layer of transparent metal oxide to a desired thickness. The source of oxygen may comprise dissolved oxygen or at least one oxygen precursor, such as at least one of dissolved nitrate, nitrite, peroxygen, ozone, traces of water. The concentration of dissolved oxygen to be prepared for the electrochemical process for forming the transparent metal oxide layer should be selected to promote formation by providing at least a sufficient source of oxygen to the volume of the second electrolyte 20 dispensed in the second kneading vessel 52. The thickness of the metal oxide layer.

The chemical composition of the second electrolyte 20 also includes a source of metal ions which is sufficiently soluble in the selected solvent and which promotes the formation of the metal transparent oxide layer to a desired thickness and such that the transparent metal oxide layer is between about 380 nm and about There is an optical transparency of about 85% to about 95% in the spectral region of the wavelength of 750 nm.

Using the above apparatus in which a transparent zinc oxide layer will be formed, the chemical in the second electrolyte may comprise a source of metal ions, such as at least one dissolved zinc salt or at least one zincate or the at least one dissolved zinc salt and A combination of at least one zincate. For example, the at least one dissolved zinc salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L (gram equivalent/liter) to 0.1 Eq/L zinc or from 0.0001 Eq/L zinc to a saturated concentration to produce a thickness of about 10 nm to about 500 nm. Zinc oxide film.

When it is desired to form a transparent non-conductive aluminum oxide layer, the metal ion source may comprise at least one dissolved aluminum salt or at least one aluminum aluminate or the at least one A combination of a dissolved aluminum salt or at least one aluminate. For example, the dissolved alumina salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L (gram equivalent/liter) to 0.1 Eq/L of aluminum or from 0.0001 Eq/L of aluminum to a saturated concentration to produce a thickness of about 10 nm to about 500 nm. Alumina film.

When it is desired to form a transparent non-conductive indium oxide layer, the metal ion source may comprise at least one dissolved indium salt. For example, the at least one dissolved indium salt can be nitric acid, chloride or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L to 0.1 Eq/L of indium or from 0.0001 Eq/L of indium to a saturated concentration to produce an indium oxide film having a thickness of about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive cadmium oxide layer, the metal ion source may comprise at least one dissolved cadmium salt. For example, the at least one dissolved cadmium salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L to 0.1 Eq/L of cadmium or from 0.0001 Eq/L of cadmium to a saturated concentration and a cadmium oxide film having a thickness of about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive magnesium oxide layer, the metal ion source may comprise at least one dissolved magnesium salt. For example, the at least one dissolved magnesium salt can be nitric acid, chloride or perchlorate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L to 0.1 Eq/L of magnesium or a magnesium to saturation concentration of 0.0001 Eq/L and a magnesium oxide film having a thickness of about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive silver oxide layer, the metal ion source may comprise at least one dissolved silver salt. For example, the at least one dissolved silver The salt can be nitric acid or perchlorate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L to 0.1 Eq/L of silver or from 0.0001 Eq/L of silver to a saturated concentration to produce a silver oxide film having a thickness of about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive cerium oxide layer, the metal ion source may comprise at least one dissolved cerium salt. For example, the at least one dissolved cerium salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L (gram equivalent/liter) to 0.1 Eq/L of hydrazine or from 0.0001 Eq/L hydrazine to a saturated concentration to produce a thickness of about 10 nm to about 500 nm. Yttrium oxide film.

When it is desired to form a transparent non-conductive cerium oxide layer, the metal ion source may comprise at least one dissolved cerium salt. For example, the at least one dissolved cerium salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L (gram equivalent/liter) to 0.1 Eq/L of rhodium or from 0.0001 Eq/L of rhodium to a saturated concentration and a thickness of about 10 nm to about 500 nm. Yttrium oxide film.

When it is desired to form a transparent non-conductive oxide layer of a lanthanide, the ion source of the lanthanide may comprise at least one dissolved lanthanide salt. For example, the at least one dissolved lanthanide salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of a lanthanide or from a 0.0001 Eq/L lanthanide to a saturated concentration to produce a lanthanide system having a thickness of from about 10 nm to about 500 nm. Elemental oxide film.

When it is desired to form a transparent non-conductive gallium oxide layer, the metal ion source may comprise at least one dissolved gallium salt. For example, the at least one dissolved state gallium The salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L to 0.1 Eq/L of gallium or from 0.0001 Eq/L of gallium to a saturation concentration to produce a gallium oxide film having a thickness of about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive oxide layer composed of a transition metal of the group IVA of the periodic table (for example, titanium, zirconium or hafnium), the ion source of the transition metal may comprise at least one dissolved metal salt. . For example, the at least one dissolved metal salt can be a chloride or a sulfate. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of transition metal or from 0.0001 Eq/L of transition metal to saturation concentration to produce a transparent metal oxide having a thickness of from about 10 nm to about 500 nm. film.

When it is desired to form a transparent non-conductive oxide layer composed of a metal of Group IVB of the periodic table (for example, antimony, tin or lead), the ion source of the suitable metal may comprise at least one dissolved metal salt. For example, the at least one dissolved metal salt can be a chloride or a sulfate. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of metal or from 0.0001 Eq/L of metal to a saturated concentration to produce a metal oxide film having a thickness of from about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive oxide layer composed of a transition metal of Group VA of the periodic table (for example, vanadium, niobium or tantalum), the ion source of the transition metal may comprise at least one dissolved transition metal salt. For example, the at least one dissolved transition metal salt can be nitric acid or chloride. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of metal or from 0.0001 Eq/L of metal to a saturation concentration to produce a thickness of about 10 nm to about 500 nm metal oxide film.

When it is desired to form a transparent non-conductive oxide layer composed of a transition metal of Group VIA of the periodic table (for example, chromium, molybdenum or tungsten), the ion source of the transition metal may comprise at least one dissolved transition metal salt. For example, the at least one dissolved transition metal salt can be a chloride or a sulfate. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of metal or from 0.0001 Eq/L of metal to a saturated concentration to produce a metal oxide film having a thickness of from about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive oxide layer composed of a transition metal of the group VIIA of the periodic table (for example, manganese or cerium), the ion source of the transition metal may comprise at least one dissolved transition metal salt. For example, the at least one dissolved transition metal salt can be a chloride or a sulfate, for example. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of metal or from 0.0001 Eq/L of metal to a saturated concentration to produce a metal oxide film having a thickness of from about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive oxide layer composed of a metal of Group VIII of the periodic table (for example, iron, cobalt, nickel or ruthenium), the ion source of the suitable metal may comprise at least one dissolved metal salt. For example, the at least one dissolved metal salt can be a chloride or a sulfate. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of metal or from 0.0001 Eq/L of metal to a saturated concentration to produce a metal oxide film having a thickness of from about 10 nm to about 500 nm.

When it is desired to form a transparent non-conductive oxide layer composed of a metal of the VB group of the periodic table (for example, ruthenium or osmium), the ion of the suitable metal The source may comprise at least one dissolved metal salt. For example, the at least one dissolved metal salt can be nitric acid, chloride or sulfate. For example, the organic solvent electrolyte solution may comprise from 0.0001 Eq/L to 0.1 Eq/L of metal or from 0.0001 Eq/L of metal to a saturated concentration to produce a metal oxide film having a thickness of from about 10 nm to about 500 nm.

The second electrolyte 20 may comprise a dopant having a concentration that causes the transparent metal oxide layer to be conductive. Selecting the dopant and the concentration of the precursor in the second electrolyte 20 thereby forming a doped transparent conductive metal oxide on the second conductive surface 30 to have a sheet resistance of between 1000 and 1.0 Ω/sq, And the transmittance in the visible light wavelength range is in the range of 60% to 100%. For example, the dopant may comprise at least one element selected from the group consisting of halogen, zinc, cadmium, magnesium, copper, silver, gold, boron, aluminum, gallium, indium, antimony, bismuth, antimony, tin. , lead, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, antimony, iron, cobalt, nickel, antimony, arsenic, antimony, antimony, platinum and other metals, and actinides.

When it is desired to form a transparent conductive aluminum-doped zinc oxide layer, the metal ion source may comprise at least one dissolved zinc salt and at least one dissolved aluminum salt. For example, the dissolved zinc salt can be nitric acid, chloride, perchlorate or sulfate. For example, the dissolved aluminum salt can be selected from the group consisting of nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may comprise zinc and aluminum in a gram equivalent ratio of between about 10,000:1 and 5:1 to produce an aluminum-doped zinc oxide film having a thickness of from about 10 nanometers to about 500 nanometers.

When it is desired to form a cerium-doped zinc oxide layer, the metal ion source may comprise at least one dissolved zinc salt and at least one dissolved cerium salt. For example, the dissolution The zinc salt may be selected from the group consisting of nitric acid, chloride, perchlorate or sulfate. For example, the dissolved cerium salt can be selected from the group consisting of nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may comprise zinc and ruthenium in a gram equivalent ratio of between about 10,000:1 and 5:1 and an antimony-doped zinc oxide film having a thickness of from about 10 nm to about 500 nm.

When it is desired to form a transparent conductive indium doped zinc oxide layer, the metal ion source may comprise at least one dissolved zinc salt and at least one dissolved indium salt. For example, the dissolved zinc salt can be nitric acid, chloride, perchlorate or sulfate, and the at least one dissolved indium salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may comprise zinc and indium in a gram equivalent ratio of between about 10,000:1 and 5:1 to produce an indium-doped zinc oxide film having a thickness of from about 10 nanometers to about 500 nanometers.

When it is desired to form a transparent conductive cadmium zinc oxide layer, the metal ion source may comprise at least one dissolved zinc salt and at least one dissolved cadmium salt. For example, the dissolved zinc salt can be nitric acid, chloride, perchlorate or sulfate, and the at least one dissolved cadmium salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may comprise zinc and cadmium in a gram equivalent ratio of between about 10:1 and 1:10 to produce a cadmium-doped zinc oxide film having a thickness of from about 10 nanometers to about 500 nanometers.

When it is desired to form a transparent conductive chlorine-doped zinc oxide layer, the metal ion source may comprise at least one dissolved zinc salt and at least one dissolved chloride. For example, the at least one zinc salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may contain 0.0001 Eq/L (gram equivalent/liter) to 0.1 Eq/L zinc or 0.0001 Eq/L zinc to a saturated solution. Concentrations and concentrations of from 0.0001 Eq/L to 0.1 Eq/L of chloride or from 0.0001 Eq/L of chloride to a saturated solution to produce a chlorine-doped zinc oxide film having a thickness of from about 10 nm to about 500 nm.

When it is desired to form a transparent conductive tin-doped indium oxide layer, the metal ion source may comprise at least one dissolved indium salt and at least one dissolved tin salt. For example, the dissolved indium salt can be nitric acid, chloride, perchlorate or sulfate, and the at least one dissolved tin salt can be selected from the group consisting of nitric acid, chloride or sulfate. For example, the organic solvent electrolyte solution may comprise indium and tin in a gram equivalent ratio of between about 200:1 and 1:1 to produce a tin-doped indium oxide film having a thickness of from about 10 nanometers to about 500 nanometers.

When it is desired to form a transparent conductive indium doped cadmium oxide layer, the metal ion source may comprise at least one dissolved cadmium salt and at least one dissolved indium salt. For example, the dissolved cadmium salt can be nitric acid, chloride, perchlorate or sulfate, and the at least one dissolved indium salt can be nitric acid, chloride, perchlorate or sulfate. For example, the organic solvent electrolyte solution may comprise cadmium and indium in a gram equivalent ratio of between about 1000:1 and 10:1 to produce an indium-doped cadmium oxide film having a thickness of from about 10 nm to about 500 nm.

The device can be used with a stationary substrate, as shown in Figure 2, but this can only be made as a transparent metal oxide layer on the second conductive surface portion 30. To this end, the first and second electrolytes 14, 16 are assembled with one of the above options to contain a chemical that will produce the desired metal oxide layer, and then the constant current power supply 108 is activated to apply electricity to the first 2. The first electrode 22, 16 causes current to flow from the second electrode 22 through the second electrolyte 20 to the second conductive surface portion 30, passing over the inner wall seal 172. The extended conductive surface 32 to the first conductive surface portion 28 then passes through the first electrolyte 14 to the first electrode 16.

FIG. 3 illustrates an equivalent circuit generally indicated by element symbol 201. The equivalent circuit includes a power supply 108 and wires 104, 132 coupled to the first and second electrodes 16, 22. The second electrode (22) is represented by a first resistor 203. The second electrolyte 20 is represented by a second resistor 205, the second conductive surface portion (30) is represented by a third resistor 207, and the first conductive surface portion (28) is represented by a fourth resistor 209 for the first electrolyte 14 The fifth resistor 211 indicates that the first electrode 16 is represented by a sixth resistor 213.

In fact, the resistors 203, 205, 207, 209, 211, and 213 are across the positive and negative ends of the power supply 108 in series such that the positive potential of the second electrode 22 is higher than the first electrode 16. This causes a voltage drop across each of the resistors to set the potential of the interface 215 of the second electrode 22 and the second conductive surface portion 30 and the interface 217 of the second electrolyte and the second conductive surface portion 30 to a higher level. The potential is to promote a cathodic chemical reaction at the interface 217 where the transparent metal oxide layer is formed. The second conductive surface portion 30 has a relatively low conductivity, so that the negative cathode potential is relatively uniform along the second conductive surface portion 30 and promotes the formation of a corresponding uniform transparent metal oxide layer on the second conductive surface portion. 30 on.

It should be understood that if there is an ion exchange path between the first electrolyte 14 and the second electrolyte 20 (the resistive current flow path represented by the resistor R7 in FIG. 3), the first and second conductive surface portions are shunted. The current surface between 28 and 30 results in a decrease in the plating efficiency of the second conductive surface. Reduced plating efficiency results in a significant reduction in resistance due to ion exchange paths. First and second The combined voltage drop of the conductive surface portions 28, 30 reduces the current flowing through the second conductive surface portion 30, reducing the amount of electron exchange at the second conductive surface portion 30 and thereby reducing the amount of electron exchange formed thereon. Transparent metal oxide layer.

Referring again to FIG. 2, in the illustrated embodiment, power supply 108 is provided with a current source 107 and means for calculating the number of charge coulombs of the current flowing through circuit 201 of FIG. Referring again to FIG. 2, the power supply 108 further includes a component for communicating with the means for calculating the Coulomb number for the charge coulomb number indicated by the member for calculating the Coulomb number to be satisfied and applied to the second conductive surface portion 30. The application of this potential is stopped when the desired thickness of the transparent metal oxide is related. The means for calculating the Coulomb number may include an amperometric meter with an integral function, such as a current shunt 109 and a processor circuit 111 for monitoring the voltage across the shunt to generate a representative current The signal of the traffic. The processor circuit 111 can include an integrating program that accumulates current signals to produce a charge coulomb value. The means for stopping the application of the potential may comprise processor circuit 111 and a code which causes processor circuit 111 to compare the charge coulomb number with a predetermined number associated with the desired thickness of the transparent metal oxide, and to activate the operational To control the output of the processor circuit 111, such as the relay 113, for interrupting the circuit to thereby stop the application of potential to the first and second electrodes 16, 20 and the current flow of the stop circuit. Alternatively or additionally, the processor circuit 111 can monitor an ionic conductivity sensor (not shown) in the second electrolyte 20 to obtain an image of the conductivity of the second electrolyte, the conductivity being in the second electrolyte The number of metal ions is proportional. The processor circuit 109 can further include a code that causes it to activate the output signal to automatically open the exhaust conduit (not shown) that is coupled to the discharge apertures 196, 198. A valve (not shown) is provided to discharge the first and second electrolytes 14 and 20. The code may also cause the processor circuit 109 to close the valve on the discharge conduit and then open a valve (not shown) on the inlet conduit (not shown) that is connected to the electrolyte introduction openings 192, 194 to allow introduction of a new The first and second electrolytes 14, 20 are within the first and second kneading containers 50, 52. The code may also instruct the processor circuit 109 to cause the relay 113 to energize to cause a potential to be applied again between the second and first electrodes 22, 16 to thereby reestablish current after the first and second electrolytes 14, 20 are replaced. flow.

Although the device 10 illustrated in Figures 1 and 2 can be used to form a transparent metal oxide layer on the second conductive surface portion 30, it should be understood that this is only a small portion of the entire conductive surface 32. In addition, it will be appreciated that since the conductive surface 32 of the dielectric substrate 34 has a relatively low conductivity, the negative cathode potential on the second conductive surface 30 is not uniform enough in the longitudinal direction to promote the formation of a corresponding uniform transparent metal oxide. The layer is on the conductive surface 32 of the dielectric substrate 34 that is actually useful in length. The large area conductive surface of the dielectric substrate can accept a uniform transparent metal oxide layer if the substrate 34 is smoothly moved with respect to the first and second electrolytes 14, 20 to expose the entire length of the substrate 34 to the second electrolyte 20 and Thereby, the conductive surface is gradually and uniformly plated. The conductivity of the conductive surface 32 of the dielectric substrate 34, the length of the first and second kneading containers 50, 52, and the linear velocity of the substrate 34 can be optimized to provide a height on a dielectric substrate having a given length. A transparent metal oxide layer of uniform thickness, optical transparency, and electrical conductivity.

Referring to FIG. 4, the device 10 can be used to form a transparent metal oxide layer over most of the conductive surface 32 of the dielectric substrate 34 by dielectric The substrate 34 moves toward the first and second electrolytes 14, 20 in a direction from the first electrolyte 14 to the second electrolyte 20 while the current is flowing to cause conductivity of the transparent metal oxide layer along the dielectric substrate 34. The longitudinal direction of the surface 32 is formed.

To facilitate relative movement of the substrate to the first and second electrolytes, the apparatus 10 is provided with a first inlet winch 220 and an entrance pinch roller 222 and an outlet winch 224 and an outlet pinch roller 226. The inlet and outlet winches 220, 224 and the pinch rollers 222, 226 have an elastically deformable outer surface to gently grip the dielectric substrate 34 and its conductive surface 32 to direct the dielectric substrate through the device 10. The inlet winch 220 is rotated clockwise and pressed against the conductive surface 32 of the dielectric substrate 34 while the inlet pinch roller 222 is pressed against the uncoated surface of the dielectric substrate 34. The dielectric substrate 34 is thus sandwiched between the inlet winch 220 and the inlet pinch roller 222 such that as the inlet winch 220 rotates, the dielectric substrate 34 is pushed into the inlet opening 70 in the direction indicated by arrow 228.

At the same time, the exit winch 224 is also rotated clockwise and pressed against the conductive surface 32 of the dielectric substrate 34 that has just been exposed to the second electrolyte 20 while the exit pinch roller 226 is pressed against the dielectric substrate. The uncoated surface of 34 causes the substrate to be sandwiched between the exit winch 224 and the exit pinch roller 226, and the linear movement of the dielectric substrate 34 can be further assisted by pulling the substrate out of the exit opening 152. This allows the conductive surface of any length of dielectric substrate to be coated with a layer of transparent metal oxide. The rotational speeds of the inlet and outlet winches 220, 224 are such that a given second surface portion 30 of the conductive substrate 32 of the dielectric substrate 34 is exposed to the second electrolyte 20 for a time sufficient to cause a desired thickness of the transparent metal oxide layer. Formed on it. With the metal ion of the second electrolyte 20 is concentrated The degree of decrease, the rotational speed of the inlet and outlet winches 220, 224 should be reduced to maintain a uniform thickness of the layer being formed until the metal ion concentration of the second electrolyte 20 reaches a predetermined metal ion concentration, at which time the following sequence is initialized: stop application Current, replace the second electrolyte, and then apply current, as described above. A series of sequences may be required, i.e., the replenishment of the second electrolyte, and the number of additions may depend on the length of the dielectric substrate on which the transparent metal oxide layer is to be formed. In the illustrated embodiment, the inlet and outlet winches 220, 224 can be rotated to create a linear motion of the substrate 34 relative to the device 10, for example, from about 0.1 cm/min to 10 cm/min.

The length of the first or second kneading container is independently optimized from the speed of movement of the dielectric substrate to form a highly uniform thickness, optical transparency, and electrical conductivity on the conductive metal oxide of the dielectric substrate of large length. .

Referring to FIG. 5, the apparatus 10 of FIG. 1 can be used in the system 250 according to the third embodiment of the present invention to form a transparent metal oxide layer from a polymer film (eg, polyethylene terephthalate (PET). Formed on the conductive surface 246 of the dielectric substrate 248. In this regard, a roll of PET film, generally illustrated at 252, is provided on mandrel 254 and is operable to rotate in a counterclockwise direction 256 and feed its leading edge into inlet opening 150 of device 10. The leading edge passes through the inlet wall 54 in a prescribed manner, over the first and second kneading containers 50, 52, and then through the outlet opening 152 of the outlet wall 62. The leading edge is then wound onto a take up spindle 258 that is also operable to rotate in a counterclockwise direction. At least the take-up mandrel 258 is driven, for example, by a motor (not shown) to pull the dielectric substrate 248 through the device 10 at a suitable speed across the first and second electrolytes 14, 20 to form a transparent metal oxide layer on the dielectric substrate. Material 248 On the conductive surface 246. Thus, a transparent metal oxide layer can be formed on the PET film pre-formed with the initial transparent conductive surface and the PET film can have any length. As mentioned above, it may be necessary to supplement the second electrolyte depending on the volume of the second electrolyte, the width and length of the film.

Figure 6 illustrates a device generally designated by the symbol 300 in accordance with a fourth embodiment of the present invention. Device 300 includes first and second end walls 304, 306, first and second side walls 308, 310 and a bottom tray 312 of deep tray container 302. An elongated opening 314 is provided in the bottom wall 312 to accommodate the heating element, as described above. The deep disc-shaped container 302 is made of a chemically stable and thermally conductive material suitable for inertly storing a volume of the initial electrolyte 316, for example, Teflon reflowed alumina. The substrate 318 to be coated with the conductive surface 320 is placed in the deep disc-shaped container 302 such that the conductive surface 320 is in contact with the initial electrolyte 316 face up. Referring to Figure 7, the deep disc-shaped container 302 has a fill opening 303 in the first end wall 304 and a discharge opening 307 in the opposite end wall 306 for filling and discharging the electrolyte, respectively.

Referring again to Figure 6, in this particular embodiment, a device similar to device 10 of Figure 2 is shown generally at 350 in an inverted position. Device 350 is similar to that of Figure 2 in that it has a generally rectangular shape and that it has inlets, outlets and inner walls 352, 354 and 356 and side walls (only one of which is shown at 358), and a bottomed wall portion 360. The bottom wall portion 360 faces up and the uppermost portion of the device because the device is in the inverted cube position as shown. However, device 350 differs from FIG. 2 in that inlet and outlet walls 352, 354 have no inlet and outlet openings and inner wall 356 is not shorter than inlet and outlet walls 352, 354. Instead, the inlet, outlet, and inner walls 352, 354, and 356 each have an elastomeric seal 368, 370. And coplanar distal surfaces 362, 364, 366 of 372. A similar seal is mounted on the coplanar distal surface of the end wall 358. Thus, a first kneading container 380 is formed between the inlet wall 352, the inner wall 356 and the end wall 358 and the bottom 360. Likewise, a second kneading container 382 is formed between the outlet wall 354, the inner wall 356, the end wall 358, and the bottom wall portion 360. The device 350 of this embodiment differs from the device of FIG. 2 in that the first and second electrodes 390, 392, each identical to the electrodes 16, 22 of FIG. 2, are illustrated as extending through the bottom wall, respectively. The elongated openings 393, 394 of the portion 360 extend into the first and second kneading containers 380, 382, respectively. The openings 393, 394 are each sealed with the same resilient seals 396, 398 of the type as the seals 76, 78 described above to prevent any electrolyte of the first and second kneading containers 380, 382 from being exposed through the bottom 360. In addition, the bottom portion 360 has at least one opening, in which case the first and second plurality of openings 400 and 402, each associated with the first and second kneading containers 380, 382, are used to lower the entry in the device 350. The deep disc-shaped container 302 releases air as explained below. The device 350 is coupled to the member 420 for placing the first and second kneading containers 380, 382 on the conductive surface 320 of the dielectric substrate 318 face down such that the substrate is within the inlet wall 352, the outlet wall 354, and The wall 356 and the first pair and the second pair of end walls 358 extend below such that the first and second conductive surface portions 422, 424 of the dielectric substrate 318 face the first and second kneading containers 380, 382, as shown The outline of the dotted line in 7 is shown. In the illustrated embodiment, the means for achieving the positioning of the device 350 is provided by a telescoping robot having a horizontally telescopic arm body 430 and a vertically extendable bracket 432.

As seen by the device 350 illustrated in dashed outline, the device is lowered into the deep tray 302 by the vertically extendable bracket 432. Deep tray 302 and device The dimensions of 350 are made such that the first pair and the second pair of end walls 358, 359 are against the inner surfaces of the top sidewalls 308, 310.

Referring to Figure 7, device 350 is lowered into deep disc-shaped container 302 until seals 368, 370 and 372 and end wall seals are in contact with conductive surface 320 of substrate 318 for the first use of substrate 318, respectively. The second conductive surface portions 422, 424 enclose the kneading containers 380, 382 to thereby establish an electrochemical cell isolated from the first and second electrolytes within the first and second kneading containers 380, 382. When the first kneading container 380 has the initial electrolyte 316 of the first volume 381 and the initial electrolyte 316 of the second kneading container 382 having the second volume 383, the first and second kneading containers 380, 382 are almost immersed in the initial The electrolyte 316 simultaneously leaves an air gap between the first volume surface and the bottom wall portion 360 and an air gap between the second volume surface and the bottom wall portion 360. Thus, seals 368, 370 and 372 and end wall seals can be used to seal inlet wall 352, outlet wall 354, inner wall 356 and first and second end walls 358 against substrate 318 conductive surface 320 for first The kneading container 380 contains the initial electrolyte 316 of the first volume 381 and the second container 382 contains the initial electrolyte 316 of the second volume 383.

The air gap allows electrolyte conditioning chemicals to be added to the first and/or second volume through openings 400, 402. For example, it may be desirable to add an acid or base to the first volume to adjust the pH of the first volume of the electrolyte to a desired value to protect the first electrode from metal oxide formation on its surface.

Referring again to FIG. 7, the power supplies 108 mentioned in the description of FIG. 2 are each connected to the first and second electrodes 390, 392 such that the second electrode 392 has a large The positive potential of the first electrode 390 thereby causing current to flow from the second electrode 392 into the second volume 383 of the electrolyte in the second kneading vessel 382, through the second conductive surface portion 424, through the conductivity below the inner wall 356 Surface 320 (not shown in Figure 7) enters first conductive surface portion 422, then enters electrolyte first volume 381 in first kneading vessel 380 and then enters first electrode 390. This causes the second conductive surface portion 424 to be more negative to the second electrode 392 such that a transparent metal oxide layer can be formed on the second conductive surface portion 424.

If the device 350 remains stationary in the tray 302, only the second conductive surface portion 424 that is in contact with the electrolyte in the second kneading container 382 will be coated. However, to apply a larger surface area, the horizontally telescoping arm body 430 can be moved in the direction of arrow 433 while the tray 302 and the dielectric substrate 318 remain stationary to move the device 350 to the Figure 7 The position of the dotted outline. The horizontally telescopic arm body 430 is movable in a direction of arrow 433 at a linear velocity of from about 0.1 cm/min to about 10 cm/min, for example, as in the first embodiment, resulting in the first and second kneading surfaces The containers 380, 382 can be in contact with the electrolyte in the second kneading container 382 from the second conductive surface portion 424, shown in solid line outline, to the final position in the final position of the device 350 (shown in phantom outline in Figure 7). The resulting second conductive surface portion 440 sweeps across the conductive surface 320 of the substrate 318 to continuously coat substantially all of the conductive surface 320. It will be appreciated that no transparent metal oxide conductive surface is formed on the final first surface portion 442 because this portion is not exposed to the second volume 383 of the electrolyte in the second kneading container 382 where the second second conduction is ultimately achieved. The potential of the surface portion 440 is more negative than the second electrode 392. Therefore, here is the concrete In the embodiment, a small portion of the conductive surface 320 on the substrate 318 (final first surface portion 442) is not coated with a transparent metal oxide.

Referring to FIG. 8, a device in accordance with a fifth embodiment of the present invention is generally indicated by reference numeral 500. Device 500 includes an electrochemical battery pack, generally indicated by reference numeral 502, and a pressing assembly, generally indicated by reference numeral 504.

Referring to the expanded view of FIG. 9, an electrochemical battery pack 502 comprising a first electrode 503 comprising a rectangular dielectric substrate 507 having a conductive surface 506 on which a transparent metal oxide layer will be formed is illustrated. . Substrate 507 has first and second end edges 508, 510 that are each coupled to jaws 512, 514. The clamps 512, 514 are like the clamp 92 of FIG. The clamps 512, 514 are electrically connected together by wires 513, 515 of the same potential and connected to the negative terminal 106 of the power supply 108 (mentioned in the description of Figure 2). The frame spacer 516 defining the space is on the conductive surface 506 of the dielectric substrate 507. For example, the housing space defined by the spacer may be formed of a soft elastomeric material, for example produced by DuPont Viton ^TM. The spacer 516 has a form matching the corresponding exposed area of the first conductive layer 506 (between the first and second clamps 512, 514 and the side (only one of which is illustrated by 518 in FIG. 9)) rectangle. Shim 516 is formed with a rectangular opening 520 defined by inner wall 522 of shim 516. Inner wall 522 defines a space 524 bounded by inner wall 522 and a portion 526 of conductive substrate 506 conductive surface 506. The shim 516 has a frame portion 528 and the frame portion 528 has first and second openings 530, 532 extending therethrough and communicating with the space 524. The openings 530, 532 each receive and retain the first and second conduits 534, 536 for receiving and discharging the electrolyte of the space 524, respectively, as described below.

The electrochemical battery 502 further includes a second electrode 505 including a second substrate 550 having a second conductive surface 552 and first and second edges 558, 560 respectively disposed on the second substrate 550 and with the second conduction The third and fourth jaws 554, 556 are in contact with the surface 552. The clamps 554, 556 are identical to the clamps 512, 514 and thus identical to the clamp 92 of FIG. The clamps 554, 556 are electrically coupled to each other by wires 555, 557 that are coupled to the positive terminal 134 of the power supply 108 as described with respect to FIG.

Referring again to FIG. 9, the second electrode 505 abuts against the flat surface 517 of the spacer 516 such that the flat surface 517 of the spacer 516 contacts the portion of the conductive surface 552 between the clamps 554, 556.

Referring again to Figure 8, the press assembly 504 includes first and second steel sheets 600, 602 that are shaped into respective surface portions, each of which is not sandwiched between the first and second substrates 504, 550. The regions occupied by the jaws 512, 514, 555, and 556 are in contact, and more shaped to have first and second outwardly extending sides, and FIG. 8 illustrates only the first outwardly extending side 604 of the first panel 600, And FIG. 8 illustrates first and second outwardly extending sides 606, 608 of the second plate 602. The first outwardly extending sides 604, 606 include first apertures 610, 612. The opening 610 of the first plate 600 is threaded and the opening 612 of the second plate 602 is smooth to receive the bolt 614 therethrough. Similar openings are provided in the second outwardly extending portion, and only the outwardly extending portion 608 in which the bolt 616 is received is illustrated in the field. The bolts 614 and 616 are identical and each has a threaded portion 618, a smooth portion 620, and a head portion 622. Bolt 614 passes through opening 612 to allow thread 618 to engage mating threads of threaded opening 610. Likewise, the bolt 616 engages a corresponding opening in the second outwardly extending side of the first and second plates 600, 602. then, The bolts 614, 616 are tightened to pull the first and second plates 600, 602 together such that the first and second conductive surfaces 506, 552 are pressed against the opposite sides of the spacer 516 thereby sealing the space 524 (see Figure 9) . Then, the electrolyte entering the space (524) with the composition mentioned above in describing the second electrolyte of the first embodiment is pumped through the first conduit 534, and air is allowed to escape through the second conduit 536 until the space (524) ) completely fill the electrolyte. Then, the power supply 108 is activated to apply an electricity between the conductive surface 506 of the dielectric substrate 507 to be coated with the transparent metal oxide and the first conductive surface 552 of the substrate 550 such that the second substrate 550 The first conductive surface 552 has a positive polarity with respect to the conductive surface 506 of the dielectric substrate 507 to cause a current to flow through the space between the first conductive surface 552 and the conductive surface 506 of the dielectric substrate 507 (524 The electrolyte in the ) causes an electrochemical reaction at the conductive surface 506 of the dielectric substrate 507 to form a transparent metal oxide layer on the conductive surface 506 of the dielectric substrate 507. As described above in describing the first embodiment, the power supply 108 has means for calculating the Coulomb number of the charge in the current and may have a member for the charge coulomb number in the representation of the Coulomb number. The application of this potential is stopped when the Coron number criterion associated with the desired thickness of the transparent metal oxide is used. Additionally, the power supply can have a means for interrupting the current when the metal ion concentration in the second electrolyte meets the metal ion concentration criteria. The apparatus may further comprise: means for removing the ion-depleted electrolyte in the space 524 by, for example, blowing air into the first conduit 534 to press the electrolyte through the second conduit 536. Alternatively or additionally, the electrolyte can be flushed out with, for example, a rinse solution (e.g., a solvent free of metal ions). Once the electrolyte is flushed, it can be introduced by pumping through the first conduit 534 as described above. The volume of electrolyte is within space 524. Then, after the electrolyte is replaced, the power supply 108 can be automatically or manually reactivated to re-establish the current.

In each of the above specific embodiments, a method and apparatus are provided for electrochemically forming a transparent metal oxide on a conductive surface of a dielectric substrate (eg, glass, polymer or ceramic material). The above described devices and methods performed thereby provide a metal oxide layer having a highly uniform thickness and a highly uniform electrical conductivity and optical transparency. Achieving a high degree of uniformity over a relatively large conductive surface of the dielectric substrate can be achieved by moving the substrate while the electrolyte remains stationary, as explained above in the first, second, third and fourth embodiments. As described, the electrolyte is moved while the substrate remains stationary, as shown in the fourth embodiment. In the case of the first, second, third and fourth embodiments, the conductive layer on the substrate is coated with a transparent metal oxide layer, and the opposite electrodes for the respective first and second electrochemical cells are hardly Deterioration.

While the specific embodiments of the invention have been described and illustrated, the specific embodiments are not to

10‧‧‧ device

12, 18, 24, 26‧‧‧ components

14‧‧‧First electrolyte

16‧‧‧First electrode

20‧‧‧Second electrolyte

22‧‧‧second electrode

36, 38‧‧‧ First and second electrochemical cells

50, 52‧‧‧ first and second kneading containers

186, 188, 190‧‧‧ heater elements

Claims (58)

A method of forming a transparent metal oxide layer on a conductive surface of a dielectric substrate, the method comprising the steps of: respectively: first and second conductive surface portions of the conductive surface of the dielectric substrate Exposing to the first and second electrolytes; forming a first conductive surface portion in contact with the first electrolyte and a first electrode in contact with the first electrolyte and spaced apart from the first conductive surface portion Forming a first electrochemical cell; forming a second conductive surface portion in contact with the second electrolyte and a second electrode in contact with the second electrolyte and spaced apart from the second conductive surface portion a second electrochemical cell; wherein the first and second electrochemical cells are electrically connected together in series by the conductive surface; and wherein the first electrolyte has a current promoting conduction through the first electrolyte without a first chemical that promotes a significant electrochemical reaction of the first electrode or the first conductive surface portion; and wherein the second electrolyte has a first layer that promotes current conduction through the second electrolyte a chemical, the second chemical comprising a non-aqueous solvent, a metal ion concentration at least sufficient to promote formation of the transparent metal oxide layer to a desired thickness, and a layer suitable for promoting formation of the transparent metal oxide layer in the second An oxygen source on the conductive surface portion; an electric current is applied between the first electrode and the second electrode such that the second electrode has a positive polarity to the first electrode to cause a current in the first a second electrode and the first electrode flow in series through the second electrolyte, the second conductive surface portion, the first conductive surface portion and the first electrolyte; such that the second electrode is sufficiently larger than A positive potential of the second conductive surface portion causes an electrochemical reaction to occur at the second conductive surface portion to form the transparent metal oxide layer on the second conductive surface portion. The method of claim 1, wherein the non-aqueous solvent is protic or aprotic. The method of claim 1 or 2, further comprising: releasing a metal capable of forming the transparent metal oxide layer optically transparent in a visible region of the electromagnetic spectrum from a salt soluble in the nonaqueous solvent; ion. The method of any one of clauses 1 to 3, further comprising: causing the second electrolyte to include a dopant electrochemically intercalating the transparent metal oxide layer to produce a conductive transparent Metal oxide layer. The method of claim 4, further comprising: incorporating a chemical additive to at least one of the first and second electrolytes. The method of any one of claims 1 to 5, further comprising: calculating a Coulomb number of the charge in the current, and satisfying a desired thickness of the transparent metal oxide layer at the charge coulomb number When a charge number criterion is associated, the application of the potential is stopped. The method of any one of claims 1 to 6, further comprising: the metal ion concentration in the second electrolyte conforms to a metal ion In the sub-concentration criterion, the current is interrupted, the second electrolyte is replaced, and the current is re-established. The method of any one of clauses 1 to 7, further comprising: when the current is flowing, the substrate is made relative to the first and second electrolytes by the first electrolyte Moving in the direction of the second electrolyte to cause the transparent metal oxide layer to be formed along the longitudinal direction of the conductive surface of the substrate. The method of any one of clauses 1 to 7, wherein the step of forming the first and second electrochemical cells comprises: storing the first electrolyte in a first kneading container and storing the same The second electrolyte is in the second kneading container. The method of claim 9, further comprising: defining the first and second sides with an inlet wall, an inner wall, an outlet wall, a plurality of first end wall portions, and a first bottom wall portion a container, thereby defining the first kneading container between the inlet wall, the inner wall, the first end wall portion and the first bottom wall portion, and thereby defining the second kneading container therein Between the wall, the outlet wall, the plurality of second end wall portions, and the second bottom wall portion. The method of claim 10, further comprising: extending the first electrode through the inlet wall, a first end wall portion or the first portion at a first position spaced parallel to the substrate a bottom wall portion and a second electrode extending through the outlet wall, a second end wall portion or the second bottom wall portion at a second position spaced parallel to the substrate. The method of any one of clauses 9 to 11, further comprising: incorporating the conduction by opening an opening in the inlet wall The dielectric substrate of the surface, and causing the substrate to extend over the first and second kneading containers such that the conductive surface faces the first and second kneading containers, wherein the first conductivity The surface portion is a portion of the conductive surface that extends over the first container, and wherein the second conductive surface portion is a portion of the conductive surface that extends over the second kneading container And wherein the method further comprises: causing a portion of the substrate to extend through an outlet opening of one of the outlet walls of the second kneading container. The method of claim 12, further comprising: causing the inlet opening and the outlet opening to be sealed against the conductive layer on the dielectric substrate to prevent the first and second electrolytes from being The inlet and the outlet opening leak. The method of claim 13, further comprising: sealing the inner wall against the conductive surface on the dielectric substrate to prevent the first and second electrolytes from being exchanged at the inner wall. The method of any one of clauses 9 to 14, further comprising: when the current is flowing, the substrate is opposed to the first and second electrolytes by the first electrolyte Moving in the direction of the second electrolyte to cause the transparent metal oxide layer to be formed along the longitudinal direction of the conductive surface of the substrate. The method of claim 15, wherein the moving comprises: moving the substrate while the first and second kneading containers remain stationary. The method of any one of clauses 9 to 11, further comprising: causing the first and second kneading containers to be placed face down The conductive surface of the dielectric substrate is such that the substrate extends under the inlet wall, the inner wall, the outlet wall, and the first and second end wall portions to cause the dielectric substrate The first and second conductive surfaces face the first and second kneading containers, wherein the first conductive surface portion is a portion of the conductive surface extending below the first kneading container And wherein the second conductive surface portion is a portion of the conductive surface that extends under the second kneading container, and wherein the method further comprises: disposing the conductive surface of the dielectric substrate A portion extends below the outlet wall of the second kneading container. The method of claim 17, further comprising: storing the dielectric substrate with the conductive surface facing up in a container for storing an initial electrolyte and causing the first and second sides thereof The step of placing the container face down on the conductive surface of the dielectric substrate comprises: causing the first and second kneading containers to substantially immerse into the initial electrolyte, and causing the inlet to be sealed against the substrate a wall, the outlet wall, the first and second end wall portions to accommodate a first volume of the initial electrolyte in the first kneading container and a second volume containing the initial electrolyte in the second kneading container . The method of claim 18, further comprising: causing the conductive surface against the dielectric substrate to seal the inner wall to prevent the first and second electrolytes from leaking under the inner wall. The method of any one of claims 9 to 12, wherein the substrate further comprises: when the current is flowing, the substrate is relative to the first and the first Two electrolytes Moving in the direction of the second electrolyte to cause the transparent metal oxide layer to be formed along the longitudinal direction of the conductive surface of the substrate. The method of claim 20, wherein the moving comprises: moving the first and second kneading containers while the substrate remains stationary. A method of forming a transparent metal oxide layer on a first conductive surface of a first dielectric substrate, the method comprising the steps of: placing a first conductive surface of the first dielectric substrate against a definition The space frame gasket is pressed onto the second conductive surface of the second dielectric substrate such that the frame defines a closed space between the first conductive surface and the second conductive surface; An opening in the frame gasket receives an electrolyte in the sealed space, the electrolyte having a chemical that promotes current conduction through the electrolyte, the chemical comprising a non-aqueous solvent, the metal ion concentration being at least sufficient to promote the transparency a metal oxide layer to a desired thickness of metal ions, and an oxygen source suitable for promoting formation of the transparent metal oxide layer on the first conductive surface; and applying an electric current to the first and second conduction The first conductive surface has a negative polarity with respect to the second conductive surface to cause a current to flow between the second conductive surface and the first conductive surface through the electrolyte It leads to the formation of a transparent metal oxide layer on the first conductive surface of an electrochemical reaction occurs at the first conductive surface. The method of claim 22, wherein the non-aqueous solvent is protic or aprotic. The method of claim 22 or 23, further comprising: releasing a metal capable of forming the transparent metal oxide layer optically transparent in a visible region of the electromagnetic spectrum from a salt soluble in the nonaqueous solvent; ion. The method of any one of clauses 22 to 24, further comprising: causing the second electrolyte to include a dopant electrochemically intercalating the transparent metal oxide layer to produce a conductive transparent Metal oxide layer. The method of claim 25, further comprising: incorporating a chemical additive into the electrolyte. The method of any one of claims 22 to 26, further comprising: calculating a Coulomb number of the charge in the current, and satisfying a desired thickness of the transparent metal oxide layer at the charge coulomb number The application of this potential is stopped when a charge coulomb number criterion is associated. The method of any one of claims 22 to 26, further comprising: interrupting the current, replacing the electrolyte, and re-establishing when the metal ion concentration in the electrolyte conforms to a metal ion concentration criterion This current. The method of any one of clauses 22 to 28, wherein the pressing step comprises: sufficiently pressing against a frame gasket for compressing the defined space to sufficiently seal the sealed space to prevent the electrolyte Leaked out of the sealed space. The method of any one of clauses 22 to 29, wherein the step of applying a potential comprises: first and second fixing the first and second conductive clamps to the first substrate Two opposite edges to The opposite edges of the first substrate are in electrical contact with the first conductive surface, and the third and fourth conductive clips are respectively secured to the third and fourth edges of the dielectric substrate to interface with the dielectric substrate The second conductive surface is in electrical contact, and the first and second clamps are coupled to a positive terminal of a current source and the third and fourth clamps are coupled to a negative terminal of the current source. A device for forming a transparent metal oxide layer on a conductive surface of a dielectric substrate, the device comprising: a member for storing a first electrolyte and a first electrode in contact with the first electrolyte; a member for storing a second electrolyte and a second electrode in contact with the second electrolyte; a method for simultaneously exposing each of the first and second conductive surface portions of the conductive surface of the dielectric substrate The first and second conductive surface portions are spaced apart from the first and second electrodes to form first and second electrochemical cells, respectively, and Thereby, the first and second electrochemical cells are electrically connected together in series by the conductive surface of the dielectric substrate; wherein the first electrolyte has a current promoting conduction through the first electrolyte without promoting a first chemical or a first electrochemically significant first chemical of the first conductive surface portion; and wherein the second electrolyte has a second chemical that promotes current conduction through the second electrolyte, the second chemical Comprises a non-aqueous solvent, the metal ion concentration is at least sufficient to promote formation of a metal ion of the transparent metal oxide layer to a desired thickness, and for the promotion of the transparent metal oxide a layer of an oxygen source formed on the second conductive surface portion; a member for applying a voltage between the first electrode and the second electrode, such that the second electrode has a positive electrode for the first electrode Characterizing to cause a current to flow in series between the second electrode and the first electrode through the second electrolyte, the second conductive surface portion, the first conductive surface portion and the first electrolyte; Having the second electrode have a positive potential sufficiently greater than the second conductive surface portion to cause an electrochemical reaction at the second conductive surface portion to form the transparent metal oxide layer on the second conductive surface portion Share. The device of claim 31, wherein the non-aqueous solvent is protic or aprotic. The device of claim 31 or 32, further comprising a metal ion which is soluble in the non-aqueous solvent and which is capable of forming the transparent metal oxide layer which is optically transparent in the visible region of the electromagnetic spectrum. . The device of any one of claims 31 to 33, further comprising causing the second electrolyte to include a dopant electrochemically intercalating the transparent metal oxide layer to produce a conductive transparent metal Oxide layer. The apparatus of any one of claims 31 to 34, further comprising a component for calculating a Coulomb number of the charge in the current, and a component for communicating with the member for calculating the Coulomb number Stopping when the charge coulomb number indicated by the member for calculating the Coulomb number satisfies one of the coulomb number criteria associated with the desired thickness of the transparent metal oxide layer The application of this potential. The apparatus of any one of claims 31 to 35, further comprising: a member for interrupting the current when the metal ion concentration in the second electrolyte conforms to a metal ion concentration criterion, A member for replacing the second electrolyte, and a member for reestablishing the current after the second electrolyte has been replaced. The device of any one of claims 31 to 36, further comprising a member for causing the substrate relative to the first and second electrolytes when the current is flowing The first electrolyte moves in the direction of the second electrolyte to cause the transparent metal oxide layer to be formed along the longitudinal direction of the conductive surface of the substrate. The device of any one of clauses 31 to 36, wherein the member for storing the first electrolyte and the first electrode comprises a first kneading container, and wherein the The second electrolyte and the member of the second electrode comprise a second kneading container. The device of claim 38, wherein the first kneading container comprises an inlet wall and an inner wall, a pair of first end walls, and a first bottom wall portion, and wherein the second kneading container comprises The inner wall and an outlet wall, a pair of second end walls, and a second bottom wall portion, wherein the first and second kneading containers have first and second end wall portions. The device of claim 39, wherein the first electrode extends through the inlet wall, at least one of the first end wall portions or at a first position spaced parallel to the substrate a first bottom wall portion, and wherein the second electrode is parallel to the conductive surface relative to the dielectric substrate The spaced second position extends through the outlet wall, at least one of the second end wall portions, or the second bottom wall portion. The device of any one of the preceding claims, wherein the member for simultaneously exposing the first and second surface portions of the conductive surface of the substrate is included in the inlet wall An inlet opening and an outlet opening in the outlet wall for receiving and positioning the dielectric substrate such that the dielectric substrate extends over the first and second kneading containers such that The first conductive surface portion faces the first kneading container and the second conductive surface portion faces the second kneading container. The device of claim 41, further comprising an inlet and outlet seal, the inlet and the outlet seal being operatively configured to seal the inlet against the conductive surface of the dielectric substrate The aperture and the outlet opening prevent the first and second electrolytes from leaking out of the inlet and the outlet opening, respectively. The device of claim 42, further comprising an inner wall seal operatively assembled to seal the inner wall against the conductive surface of the dielectric substrate to prevent The first and second electrolytes are exchanged at the inner wall. The device of any one of claims 38 to 43 further comprising a member for causing the substrate to be relative to the first and second electrolytes when the current is flowing An electrolyte moves in the direction of the second electrolyte to cause the transparent metal oxide layer to be formed along the longitudinal direction of the conductive surface of the substrate. The device of claim 44, wherein the component for moving A member for moving the substrate and a member for holding the first and second kneading containers stationary while the substrate is moving. The device of any one of claims 39 to 40, further comprising a member for positioning the conduction of the first and second kneading containers on the dielectric substrate face down The substrate is such that the substrate extends under the inlet wall, the inner wall, the outlet wall, and the first pair and the second pair of end walls, such that the first and second conductivity of the dielectric substrate The surface faces the first and second kneading containers. The device of claim 46, further comprising: a member for storing a volume of an initial electrolyte; and storing the dielectric substrate in the initial electrolyte with the conductive surface facing up a member; and wherein the member for positioning the first and second kneading containers face-down on the conductive surface of the dielectric substrate comprises for causing the first and second faces a member substantially immersed in the initial electrolyte; and a member for sealing the inlet wall, the outlet wall, and the first and second end walls against the substrate to accommodate the first volume of the initial electrolyte A second volume in the first kneading container and containing the initial electrolyte is in the second kneading container. The device of claim 47, further comprising a member for sealing the inner wall against the conductive surface of the dielectric substrate to prevent the first and second electrolytes from leaking out of the inner wall. The device of any one of claims 45 to 47, further comprising a member for causing the substrate relative to the first and second electrolytes when the current is flowing The first electrolyte moves in the direction of the second electrolyte to cause the transparent metal oxide layer to be formed along the longitudinal direction of the conductive surface of the substrate. The device of claim 49, wherein the member for moving comprises a member for moving the first and second kneading containers, and for the first and second kneading containers being A member that keeps the substrate stationary while moving. A device for forming a transparent metal oxide layer on a first conductive surface of a first dielectric substrate, the device comprising: positioning on the first conductive surface of the first dielectric substrate a frame gasket for defining a space, the gasket having an inner wall defining a space bounded by the inner wall and a portion of the first conductive surface of the first dielectric substrate a second substrate having a second conductive surface; a first conductive surface for pressing against the first substrate with the frame gasket for the defined space to cause the space to be sealed a member of the space; the opening in the frame gasket for incorporating an electrolyte in the sealed space, the electrolyte having a chemical that promotes current conduction through the electrolyte, the chemical comprising a non-aqueous solvent, a metal ion, and An oxygen source adapted to promote formation of the transparent metal oxide layer on the first conductive surface; a member for applying a second electrode between the second conductive surface of the second dielectric substrate and the first conductive surface of the first substrate, such that the first conductive of the first substrate The surface has a negative polarity for the second conductive surface of the second dielectric substrate to cause a current to flow between the second conductive surface and the first conductive surface to pass through the electrolyte to cause A conductive surface undergoes an electrochemical reaction to form the transparent metal oxide layer on the first conductive surface. The device of claim 51, wherein the non-aqueous solvent is a protic or aprotic solvent. The device of claim 51 or 52, further comprising a metal ion which is soluble in the non-aqueous solvent and which is capable of forming the transparent metal oxide layer which is optically transparent in the visible region of the electromagnetic spectrum. . The apparatus of any one of clauses 51 to 53, further comprising causing the second electrolyte to include a dopant electrochemically intercalating the transparent metal oxide layer to produce a conductive transparent metal Oxide layer. A device according to claim 53 or 54 further comprising a component for calculating a Coulomb number of the charge in the current, and a member for communicating with the member for calculating the Coulomb number for use in The application of the potential is stopped when the number of charge coulombs indicated by the member of the Coulomb number satisfies one of the Coulomb number criteria associated with the desired thickness of the transparent metal oxide layer. The device of any one of claims 52 to 55, further comprising: a member for interrupting the current when the metal ion concentration in the electrolyte meets the metal ion concentration criterion, for replacement The electrolysis A component of the mass and a component for reestablishing the current after the electrolyte is replaced. The device of any one of clauses 52 to 56, wherein the member for pressing is operatively assembled to compress the frame gasket for the defined space to sufficiently seal the sealed space In order to prevent the electrolyte from leaking out of the sealed space. The device of any one of clauses 51 to 57, wherein the member for applying a potential comprises each of the first and second opposite edges of the first substrate and the first conduction First and second conductive clamps electrically contacting the opposite sides of the first substrate, and opposite the dielectric substrate on the third and fourth opposite edges of the dielectric substrate The third and fourth conductive clamps of the second conductive surface electrically contacting the side, wherein the first and the second clamp are operably assembled to be connected to a negative end of a current source, And wherein the third and fourth clamps are operatively assembled to be coupled to a positive terminal of the current source.