Composition And Conductor Formed Therefrom

FIELD OF THE INVENTION

The present invention generally relates to a composition, and more specifically to a composition and to a conductor formed from the composition.

BACKGROUND

Front and rear surface metallization is an important aspect of photovoltaic (PV) cells which allows for collection and transport of charge carriers. In front PV cell constructs, the metallization is generally in the form of a grid, which includes narrow lines or “fingers” of conductive material which connect to wider busbars. Tabbing, e.g. ribbon, is soldered to the busbars to connect multiple PV cells together (e.g. in series). Typically, the grid is formed using pastes which include silver (Ag) as a primary component due to its excellent conductivity. In rear PV cell constructs, the metallization is generally in the form of an electrode (e.g. a layer of aluminum), which typically includes contacts formed from Ag. The contacts are disposed through the rear layer. The contacts can be in the form of busbars or pads.

Metallization relying on Ag is often used in other applications as well, such as in circuit boards or other applications requiring conductive material for current transport and/or electrical connection. Unfortunately, such metallization makes up a substantial portion of overall manufacturing cost due to reliance on Ag. As such, there remains an opportunity to provide improved compositions and conductors formed therefrom which are suitable for current transport and/or electrical connection in a variety of applications.

SUMMARY OF THE INVENTION

The present invention provides a composition comprising a metal powder. The composition further comprises a solder powder which has a lower melting temperature than a melting temperature of the metal powder. The composition further comprises a polymer and a carboxylated-polymer different from the polymer. The carboxylated-polymer is useful for fluxing the metal powder and cross-linking the polymer. The composition further comprises a dicarboxylic acid and a monocarboxylic acid for fluxing the metal powder. The composition may be used for forming a conductor. The conductor may be used for current transport and/or electrical connection. As such, the conductor can be useful for a variety of applications, such as being configured as a busbar, a contact pad, an electrode, etc.

The present invention also provides an article including the conductor formed from the invention composition. The article comprises a substrate and the conductor disposed on and in electrical contact with the substrate. The article may be used for various applications, such as for converting light of many different wavelengths into electricity.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention may be readily appreciated, as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein:

FIG. 1 is a diagram illustrating the polymers curing and solder reflow of the composition during formation of the conductor;

FIG. 2 is a magnified cross-sectional side view of the composition after forming the conductor illustrating polymers after cure, solder after reflow, metal particles, and an inter-metallic layer between the solder and metal particles;

FIG. 3A is a front view of an embodiment of the PV cell including a base substrate, a passivation layer, fingers, and a pair of busbars;

FIG. 3B is a rear view of the embodiment of the PV cell including the base substrate, a first electrode, and three sets of second electrodes configured as contact pads;

FIG. 4 is a partial cross-sectional side view taken along line 4-4 of FIG. 3A illustrating an upper doped region of the base substrate, the passivation layer, fingers, and one of the busbars;

FIG. 5 is a cross-sectional side view of an embodiment of the PV cell illustrating upper and rear doped regions of a base substrate, a passivation layer, fingers, a busbar, a first electrode, and a set of second electrodes;

FIG. 6 is a partial cross-sectional side view taken along line 6-6 of FIG. 3B illustrating a rear doped region of the base substrate, the first electrode, and a second electrode;

FIG. 7 is a partial cross-sectional side view of an embodiment of the PV cell illustrating a rear doped region of a base substrate, a grid or array of first electrodes, a passivation layer, and a second electrode;

FIG. 8 is a partial cross-sectional side view of an embodiment of the PV cell illustrating a rear doped region of a base substrate, a first electrode having localized contacts, a passivation layer, and a second electrode;

FIG. 9 is a partial cross-sectional side view of an embodiment of the PV cell illustrating a base substrate having localized rear doped regions, a first electrode having localized contacts, a passivation layer, and a second electrode;

FIG. 10 is a partial cross-sectional perspective view of an embodiment of the PV cell illustrating upper and rear doped regions of a base substrate, a passivation layer, fingers, a first electrode, a pair of busbars, and a pair of second electrodes;

FIG. 11 is the PV cell of FIG. 10 and a pair of tabbing ribbons with one of the tabbing ribbons being disposed on one of the busbars of the PV cell;

FIG. 12 is a schematic front view of an embodiment of the PV cell including a passivation layer, discontinuous-fingers, and a busbar;

FIG. 13 is a schematic front view of an embodiment of the PV cell including a passivation layer, discontinuous-fingers, supplemental fingers, and a busbar;

FIG. 14 is a schematic front view of an embodiment of the PV cell including a passivation layer, fingers, a busbar, and supplemental busbar pads;

FIG. 15 is a schematic front view of an embodiment of the PV cell including a passivation layer, fingers, a pair of busbars, and a supplemental busbar;

FIG. 16 is a schematic front view of an embodiment of the PV cell including a passivation layer, fingers having pads, and a busbar;

FIG. 17 is a schematic front view of an embodiment of the PV cell including a passivation layer, fingers having hollow pads, and a busbar;

FIG. 18 is a schematic front view of an embodiment of the PV cell including a passivation layer, discontinuous-fingers, supplemental fingers, and a busbar;

FIG. 19A is a schematic rear view of an embodiment of the PV cell including a base substrate, a first electrode defining a hole, and a second electrode disposed over the first electrode and in contact with the base substrate via the hole;

FIG. 19B is a schematic side view of the PV cell of FIG. 19A;

FIG. 20A is a schematic rear view of an embodiment of the PV cell including a base substrate, a first electrode defining a plurality of holes, and a second electrode disposed over the first electrode and in contact with the base substrate via the holes;

FIG. 20B is a schematic side view of the PV cell of FIG. 20A;

FIG. 21 is a schematic rear view of an embodiment of the PV cell including a base substrate; interdigitated fingers, and a pair of busbars;

FIG. 22 is a scatter plot illustrating peel force of invention examples on a silicon substrate;

FIG. 23 is a scatter plot illustrating peel force of invention examples on an aluminum substrate;

FIG. 24 is a scatter plot illustrating resistivity of invention examples;

FIG. 25 is a box graph illustrating short-circuit current density (J_SC) of comparative and invention examples;

FIG. 26 is a box graph illustrating open-circuit voltage (V_OC) of comparative and invention examples;

FIG. 27 is a box graph illustrating cell efficiency (NCell) of comparative and invention examples;

FIG. 28 is a box graph illustrating NCell of comparative and invention examples;

FIG. 29 is a box graph illustrating V_OCof comparative and invention examples with ethylene vinyl acetate and silicone encapsulants;

FIG. 30 is a graph illustrating I-V (or I-U) characteristics of comparative and invention examples with amps (A) and volts (V);

FIG. 31A is a cross-sectional SEM micrograph (converted to drawing form) of an invention example illustrating the polymers after cure, the solder after reflow, metal particles, and an inter-metallic layer between the solder and metal particles;

FIG. 31B is a cross-sectional SEM micrograph which the drawing of FIG. 31A is based;

FIG. 32 is a box graph illustrating efficiency percentage of comparative and invention examples;

FIG. 33 is another box graph illustrating J_SCof comparative and invention examples;

FIG. 34 is another box graph illustrating V_OCof comparative and invention examples;

FIG. 35 is a cross-sectional optical microscopy photograph (converted to drawing form) illustrating a tabbed busbar of the invention, a finger, and a passivation layer;

FIG. 36 is a line graph illustrating J_SCof comparative and invention examples after damp heat aging;

FIG. 37 is a line graph illustrating V_OCof comparative and invention examples after damp heat aging; and

FIG. 38 is a line graph illustrating sheet resistivity (rs) of comparative and invention examples after damp heat aging.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a composition. The composition generally comprises a metal powder, a solder powder, a polymer, a carboxylated-polymer different from the polymer, a dicarboxylic acid, and a monocarboxylic acid. In further embodiments, the composition consists essentially of, or alternatively consists of, the aforementioned components. In certain embodiments, the composition can further comprise one of more additives, described further below. The composition is useful for forming a conductor. Typically, the conductor is formed by heating the composition, as described further below. The conductor may also be referred to as an electrical conductor, which is electrically conductive. While not limited to a particular configuration or use, the conductor can be in various forms, such as busbars, fingers, pads, dots, and/or other electrode structures. Some of these are described in greater detail hereinafter.

The metal powder can comprise various metals. Typically, the metal powder has a melting temperature (or melting point; MP) that is over about 600, over about 700, over about 800, or over about 900, ° C. The metal generally has excellent electrical conductivity. In certain embodiments, the metal powder comprises at least one metal selected from the group of copper (Cu), gold, silver (Ag), zinc, aluminum, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron, molybdenum, tungsten, and/or an alloy of two or more of these metals. In various embodiments, the metal comprises a mixture (or blend) of metal particles (the same as or different from each other), and/or particles comprising two or more different metals. The latter type of particles may be alloys of two or more different metals, and/or coated particles having a core comprising at least one metal and one or more outer layers comprising at least one metal different from the core metal(s). An example of such a coated particle is a silver coated (or plated) copper particle.

In certain embodiments, the composition is substantially to completely free of “heavy” metals. Said another way, the composition typically comprises less than 0.5, less than 0.25, less than 0.1, less than 0.5, approaching zero (0), or 0, weight percent (wt %) heavy metal(s), each based on the total weight of the composition. Examples of heavy metals include mercury, cadmium, lead, and chromium. In certain embodiments, the composition is free of mercury, cadmium, and chromium. In further embodiments, the composition is free of solder powders comprising lead (Pb).

The metal powder may be treated with a stability enhancer and/or surface protectant. Such treatments can include organic chelation agents, such as azoles, e.g. benzotriazole, imidazoles, etc. Generally, decomposition products of such azoles can serve as catalysts for a reaction between the polymer and the carboxylated-polymer to form the conductor from the composition. Such a reaction generally obviates any need for post-curing of the conductor after formation.

In certain embodiments, the metal powder comprises Cu, or is Cu powder. Various types of Cu powder can be utilized. For example, Cu powder may include a surface treatment as described above. The metal powder can be of various sizes. Typically, the metal powder has a particle size of from about 0.05 to about 25, about 5 to about 25, about 5 to about 15, or about 10, μm on average. Various particle size distributions (PSDs) can be utilized, including unimodal, bimodal, or multimodal distributions, with unimodal being typical for fluxing purposes. Suitable Cu powders are commercially available from a variety of suppliers, such as Mitsui Mining & Smelting Co., Ltd., of Japan, e.g. 1030 Cu powder or Y1400 Cu powder.

The solder powder has a lower melting temperature (i.e., melting point) than a melting temperature of the metal powder. Such temperatures for the metal powder are described above. In certain embodiments, the solder powder has a melting temperature of no greater than about 300, no greater than about 275, no greater than about 250, or no greater than about 225, ° C.

Typically, the solder powder includes at least one metal selected from the group of tin (Sn), bismuth, zinc, gallium, indium, tellurium, thallium, antimony, selenium, and/or an alloy of two or more of these metals. In various embodiments, the solder powder comprises Sn, or at least one Sn alloy. In certain embodiments, the solder powder comprises two different alloys, alternatively more than two different alloys. For example, the solder powder can comprise a tin-bismuth (SnBi) alloy, a tin-silver (SnAg) alloy, or a combination thereof. The “combination” may simply be a combination of different metals, different alloys, or different metal(s) and alloy(s). In other embodiments, the solder powder may comprise Sn Pb.

In certain embodiments, the solder powder comprises Sn42/Bi58, Sn96.5/Ag3.5, or a combination thereof. Such alloy nomenclature generally indicates the amount of each metal by mass. Sn42/Bi58 generally has a melting temperature of about 138° C., and Sn96.5/Ag3.5 generally has a melting temperature of about 221° C. These alloys may be referred to in the art as “Alloy 281” and “Alloy 121”, respectively. Typically, the solder powder has a particle size of from about 0.05 to about 25, about 2.5 to about 25, about 5 to about 20, about 5 to about 15, or about 10, μm on average. Various PSDs, and modes thereof, can be utilized. Suitable solder powders are commercially available from a variety of suppliers, such as Indium Corporation of America of Elk Grove Village, Ill.

The solder is useful for suppressing oxidation of the metal powder, especially after formation of the conductor. It is believed that the solder also enhances wetting of supplemental solders and facilitates strong solder joint formation during soldering operations employing the conductor. As described further below, the solder powder, upon melting, generally fuses particles of the metal powder together prior to the composition reaching a final cure state. Such melting and fusing forms electrically conductive bridges in the conductor during formation.

The metal and solder powders can be present in the composition in various amounts. Typically, the metal and solder powders are collectively present in an amount (or a combined amount) of from about 50 to about 95, about 80 to about 95, about 80 to about 90, or about 85, wt %, each based on the total weight of the composition Typically, the metal powder is present in the composition in an individual amount of from about 35 to about 85, about 35 to about 65, about 40 to about 55, about 40 to about 50, or about 45, wt %, each based on the total weight of the composition. Typically, the solder powder is present in the composition in an individual amount of from about 25 to about 75, about 25 to about 55, about 30 to about 50, about 35 to about 45, or about 40, wt %, each based on the total weight of the composition.

The polymer can comprise various types of polymers, or a monomer which is polymerisable to yield the polymer. The polymer is generally a thermosetting resin, such as an epoxy, an acrylic, a silicone, a polyurethane, or combinations thereof. In certain embodiments, the polymer comprises an epoxy resin, which could also be a “B stage” resin. Examples of epoxy resins include diglycidyl ethers of bisphenol A, and diglycidyl ethers of bisphenol F.

In embodiments where the polymer comprises (or is) an epoxy resin, the epoxy resin can be of various epoxide equivalent weights (EEW). In certain embodiments, the epoxy resin has an EEW of from about 20 to about 100,000, about 30 to about 50,000, about 35 to about 25,000, about 40 to about 10,000, about 150 to about 7,500, about 170 to about 5,000, about 250 to about 2,500, about 300 to about 2,000, about 312 to about 1,590, about 400 to about 1,000, or about 450 to about 600, g/eq. EEW may be determined via methods understood in the art, such as by ASTM D1652.

Suitable examples of epoxy resins are commercially available from Dow Chemical of Midland, Mich., under the trademark D.E.R.™, such as D.E.R.™ 383, 6116, 662 UH, 331, 323, 354, 736, 732, 324, 353, 667E, 668-20, 671-X70, 671-X75, 684-EK40, 6225, 6155, 669E, 660-MAK80, 660-PA80, 337-X80, 337-X90, 660-X80, 661-A80, 671-PM75, 3680-X90, 6510HT, 330, 332, 6224, 6330-A10, 642U, 661, 662E, 663U, 663UE, 664U, 672U, 664UM, 667-20, 669-20, 671-R75, 671-T75, 671-XM75, and/or 692H. Other suitable epoxy resins are commercially available from Huntsman and Momentive under the trademarks Araldite® and Epikote™.

The polymer generally functions as a binder which improves the adherence of the conductor to a substrate after curing, and increases overall cohesive strength of the conductor. In general, the conductor has excellent adhesive and cohesive properties. It is believed that during/after cure, the polymer provides adhesion between the conductor and the substrate at an interface (or interfaces) there between, and also provides cohesion between internal components of the conductor, e.g. the metal powder. The polymer can stick to a variety of difference surfaces, including solderable and non-solderable surfaces. The polymer also presents a portion of the metal powder opposite the substrate interface for direct soldering purposes, e.g. for tabbing. Prior to reaching a final cure state, the polymer also acts as a medium for delivering fluxes to the metal powder, as described further below.

The carboxylated-polymer can comprise various types of polymers and copolymers having one or more carboxyl (—COOH) groups, typically two or more carboxyl groups, such that the conductor generally has a cross-linked structure. The —COOH group (or groups) generally act as flux, are reactive with other groups in the composition (e.g. epoxy groups of the polymer), and/or form salts with metal oxides thus promoting cure (e.g. catalyzing epoxy cure). Examples of these carboxylated-polymers include those resulting from the polymerization or co-polymerization via anionic mechanism or radical mechanism of unsaturated aliphatic or aromatic acids, possibly in combination with unsaturated aliphatic or aromatic hydrocarbons, such as alkenes, alkynes, and/or arylenes. Suitable unsaturated carboxylic acids include aliphatic carboxylic acids, such as methacrylic acid, halogenoacrylic acid, crotonic acid, carboxyethylacrylate, acrylic acid, fumaric acid, itaconic acid, muconic acid, propargylacetic acid, and/or acetylendicarboxylic acid; and unsaturated aromatic acids, such as vinylbenzoic acid and/or phenylpropynoic acid. Suitable unsaturated alkenes in combination with unsaturated acids to form carboxylated copolymers include propylene, isobutylene, vinylchloride, and/or styrene. Other examples of suitable carboxylated-polymers include carboxylic acid functional polyester resins and carboxylic acid anhydrides and polymers made thereof.

The carboxylated-polymer can be of various acid equivalent weights (AEW). In certain embodiments, the carboxylated-polymer has an AEW of from about 20 to about 100,000, about 25 to about 50,000, about 30 to about 25,000, about 30 to about 10,000, about 30 to about 5,000, about 30 to about 2,500, about 30 to about 2,000, about 40 to about 1,000, or about 50 to about 500, g/eq. AEW may be determined via methods understood in the art, such as by dividing molecular weight by the number of carboxyl groups and/or by ASTM D1980 to determine an acid value.

The carboxylated-polymer is useful for fluxing the metal powder and for cross-linking the polymer to form the conductor. Specifically, during heating of the composition to form the conductor, the carboxylated-polymer generally fluxes the metal powder at a first temperature, and serves as a cross-linking agent for the polymer at a second temperature, which is generally higher than the first temperature. These temperatures can vary, but generally fall within the temperature ranges described herein.

While serving as a fluxing agent for the metal powder, the carboxylated-polymer generally dissolves metal oxide on the surface of the metal. Removal of the metal oxide permits the metal particles to group (or agglomerate) and better form conductive bridges in the conductor during formation, especially in the case of solder-Cu bonding. Typically, the metal powder is fluxed in-situ during formation of the conductor, such that pre-fluxing of the metal powder prior to use is not necessary. For example, a pre-fluxer/cleaner, e.g. an acid, is not required to remove oxides from surface of the metal powder prior to use in the composition. In certain embodiments, the invention lacks prefluxer/prefluxing.

Furthermore, the removed metal oxide is generally present in sufficient quantity to catalyze the reaction between the polymer and the carboxyl groups of the carboxylated-polymer at elevated temperatures. The metal oxide can initially be imparted by heating the metal powder, which oxidizes to form oxides. The oxides can react with the carboxylated-polymer to from salts. The oxides and salts can serve as catalysts for the reaction of the polymer and carboxylated-polymer. Additionally catalysts may be made available with the thermal release of chelating agent which may have been used to treat the metal powder(s). Various catalysts can be liberated based on the type of metal and/or solder powder, such as organic tin and copper salts, benzotriazole, imidazole, etc. These various mechanisms generally occur after application of the composition and during formation of the conductor. These mechanisms interrelate to melting, wet-out, fluxing, and cure temperatures or profiles of the composition/components thereof.

In certain embodiments, the carboxylated-polymer comprises an acrylic polymer. In further embodiments, the carboxylated-polymer comprises a styrene-acrylic copolymer. In specific embodiments, the carboxylated-polymer is thermally stable at 215° C., has an acid number greater than 200, and/or a viscosity of less than 0.01 Pa·s (10 centipoise) at 20° C. Examples of suitable acrylic polymers are commercially available from BASF Corp. of Florham Park, N.J., under the trademark Joncryl®, such as Joncryl® 50, 60, 61, 63, 67, 74-A, 77, 89, 95, 142, 500, 504, 507, 508, 510, 530, 537, 538-A, 550, 551, 552, 556, 558, 581, 585, 587, 611, 624, 631, 633, 646, 655, 660, 678, 680, 682, 683, 690, 693, 690, 693, 750, 804, 815, 817, 819, 820, 821, 822, 843, 845, 848, 901, 902, 903, 906, 906-AC, 909, 911, 915, 918, 920, 922, 924, 934, 935, 939, 942, 945, 948, 960, 963, 1163, 1520, 1522, 1532, 1536, 1540, 1610, 1612, 1655, 1670, 1680, 1695, 1907, 1908, 1915, 1916, 1919, 1954, 1980, 1982, 1984, 1987, 1992, 1993, 2153, 2178, 2350, 2561, 2570, 2640, 2646, 2660, 2664, 8383, and/or HR 1620.

Typically, the polymer and the carboxylated-polymer are collectively present in the composition an amount of from about 2.5 to about 10, about 2.5 to about 7.5, about 3 to about 6, about 5 to about 6, or about 5.5, wt %, each based on the total weight of the composition. In certain embodiments, the polymer and carboxylated-polymer are in a weight ratio of from about 1:1 to about 1:3, about 1:1 to about 1:2.75, about 1:1 to about 1:2.5, or about 1:1.5 to about 1:2.5, (polymer:carboxylated-polymer).

Typically, the polymer is present in the composition an amount of from about 0.5 to about 5, about 1 to about 2.5, about 1.5 to about 2, or about 1.75, wt %, each based on the total weight of the composition. Typically, the carboxylated-polymer is present in the composition an amount of from about 1 to about 7.5, about 2 to about 5, about 3 about 4, or about 3.5 to about 4, wt %, each based on the total weight of the composition.

The dicarboxylic acid is also useful for fluxing the metal powder, in addition to the carboxylated-polymer. Various types of dicarboxylic acids can be utilized. Examples of suitable dicarboxylic acids include linear, cyclic, aromatic and/or highly branched alkyl and/or unsaturated aliphatic and/or aryl dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, glutaconic acid, traumatic acid, muconic acid, phthalic acid, isophthalic, and/or terephthalic acid. In certain embodiments, the dicarboxylic acid is dodecanedioic acid (DDDA). Typically, the dicarboxylic acid is present in the composition in an amount of from about 0.05 to about 1, about 0.1 to about 0.75, about 0.2 to about 0.5, or about 0.2 to about 0.3, wt %, each based on the total weight of the composition.

The monocarboxylic acid is also useful for fluxing the metal powder, in addition to the carboxylated-polymer and the dicarboxylic acid. Specifically, the monocarboxylic is useful for preventing premature cure of the composition from metal oxides that may be already present or formed at ambient temperature. Various types of monocarboxylic acids can be utilized. Examples of suitable monocarboxylic acids include linear, cyclic, aromatic and/or highly branched alkyl and/or unsaturated aliphatic and/or aryl monocarboxylic acids such as formic acid, acetic acid, halogenoacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, decanoic acid, palmitic acid, stearic acid, icosanoic acid, isobutyric acid, isopentanoic acid, neopentanoic acid, neodecanoic acid, isostearic acid, oleinic acid, nervonic acid, linoleic acid octynoic acid, benzoic acid, and/or phenylpropynoic acid. In various embodiments, the monocarboxylic acid is a versatic acid. In certain embodiments, the monocarboxylic acid is Versatic 10, which is a synthetic acid comprising a mixture of highly branched isomers of C₁₀monocarboxylic acids, mostly of tertiary structure. Versatic 10 may also be referred to in the art as neodecanoic acid. Examples of suitable monocarboxylic acids are commercially available from Hexion Specialty Chemicals of Carpentersville, Ill.

It is believed that the high degree of branching in the monocarboxylic acid gives rise to steric hindrance which imparts salts formed therefrom with excellent stability. In certain embodiments, the monocarboxylic acid is liquid at room temperature (RT; ˜20 to 25° C.). Typically, the monocarboxylic acid is present in the composition an amount of from about 0.25 to about 1.25, about 0.25 to about 1, about 0.25 to about 0.75, about 0.4 to about 0.5, or about 0.45, wt %, each based on the total weight of the composition.

In embodiments where the polymer comprises an epoxy resin such that epoxy groups are provided, the ratio of acidic groups (provided by the acids) to epoxy groups is generally of from about 1:1 to about 10:1, about 2:1 to about 9:1, about 3:1 to about 8:1, about 4:1 to about 7:1, about 5:1 to about 7:1, or about 6:1 to about 7:1, acidic:epoxy (A:E). In further embodiments, the ratio of acidic groups to epoxy groups is generally at least about 3:1, at least about 3.5:1, at least about 4:1, at least about 4.5:1, at least about 5:1, at least about 5.5:1, at least about 6:1, at least about 6.5:1, or at least about 7:1, A:E.

Without being bound or limited to any particular theory, it is believed that increasing the A:E ratio, e.g. above about 4:1, provides for excellent fluxing of the metal powder without the need for pre-fluxing of the metal powder. At lower ratios, e.g. less than about 4:1 A:E, it is believed that the composition will not be directly solderable due to insufficient fluxing of the metal powder. Specifically, in certain embodiments, at a A:E below about 4:1, fluxing may not occur, which can be determined via color change during heating/cure. In addition, at such lower levels, the solder powder may not wet out and/or be solderable, even with fluxing. Generally, a color change (or shift) from brown to light to dark grey indicates sufficient fluxing or fluxed materials. As such, if the material remains brown (or brown like, e.g. coppery colored) after attempting to flux the material, then fluxing did not occur or was insufficient. It is believed that the material turns grey after fluxing due to wetting out of the metal powder, e.g. Cu, surface with the solder such that you effectively only see the solder. In situations where fluxing is insufficient, the surface of metal powder is not completely wet out with the solder such that it is still visible.

In certain embodiments, the composition can further comprise an additive. Various types of additives can be utilized. Examples of suitable additives include solvents, adhesion promoters, defoamers, deactivators, anti-oxidants, rheology enhancers/modifiers, and/or thermal agents. Further examples of suitable components, useful for forming various embodiments of the composition, are disclosed in U.S. Pat. No. 7,022,266 to Craig, and in U.S. Pat. No. 6,971,163 to Craig et al., both of which are incorporated herein by reference in their entirety to the extent they do not conflict with the general scope of the invention.

If utilized, solvents can be useful for cutting the polymer and/or carboxylated-polymer into solution. Solvents can also be useful for adjusting viscosity of one or more of the components, and/or for adjusting rheology of the composition itself. Adjusting viscosity of the composition can be useful for various purposes, e.g. for obtaining a desired viscosity should the composition be applied via printing or similar technique. Various types of solvents can be utilized. Examples of suitable solvents include alcohols, such as monoterpene alcohol (e.g. terpineol), and benzyl alcohol. Further examples include 2-ethoxyethyl acetate, 2(3)-(Tetrahydrofurfuryloxy)tetrahydropyran, diisobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol-1,2 propanediol. Such solvents are commercially available from various sources, such as Sigma Aldrich of Chicago, Ill. Another suitable solvent is butyl carbitol, which is commercially available from Dow Chemical. Various combinations of solvents can be utilized. The solvent can be used in various amounts. In certain embodiments, the solvent(s) is present in the composition in an amount of from about 0.5 to about 15, about 1 to about 12.5, about 2.5 to about 10, about 5 to about 7.5, or about 5 to about 7, wt %, each based on the total weight of the composition. Depending on application technique, the solvent may be added in a predetermined amount and/or added as needed.

If utilized, adhesion promoters are useful for further increasing adhesion of the conductor on various substrates. Various types of adhesion promoters can be utilized. Examples of suitable adhesion promoters (or coupling agents) include those based on silane and/or titanate. Employing silane adhesion promoters is useful for increasing adhesion to substrates having organic functionalities. Employing titanate adhesion promoters is useful for increasing adhesion to substrates having inorganic fillers. It is believed that the titanate coupling agent couples to the surface of inorganic fillers to improve the compatibility with an organic matrix and also improves adhesion to the substrate. A combination of different promoters can be used. In certain embodiments, the adhesion promoter, e.g. titanate, is reactive with at least one of the polymers of the composition. Examples of suitable adhesion promoters are commercially valuable from Dow Corning Corp. of Midland, Mich., such as 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane, e.g. Z-6043, or glycidoxypropyltrimethoxysilane, e.g. Z-6040. Further suitable examples include those commercially available from Momentive under the trademark Silquest, such as Silquest A-187; from Xiameter, such as Xiameter® OFS-6040; and from Kenrich Petrochemicals Co. of Bayonne, N.J., under the trademark Ken-React®, such as Ken-React® KR9S. While not required, the adhesion promoter can be used in various amounts. In certain embodiments, the adhesion promoter(s) is present in the composition in an amount of from about 0.01 to about 3, about 0.1 to about 2, about 0.25 to about 1, or about 0.8, wt %, each based on the total weight of the composition.

If utilized, defoamers are useful for preventing foaming during formation and/or use of the composition. Various types of defoamers can be utilized. Examples of suitable defoamers include silicone-free defoamers. Examples of suitable defoamers are commercially available from BYK additives & instruments of Wallingford, Conn., such as BYK®-052. While not required, the defoamer can be used in various amounts. In certain embodiments, the defoamer(s) is present in the composition in an amount of from about 0.01 to about 1, about 0.1 to about 0.75, about 0.1 to about 0.5, or about 0.1 to about 0.3, wt %, each based on the total weight of the composition.

If utilized, deactivators and/or anti-oxidants are useful for suppressing migration of metals, e.g. Cu. Various types of deactivators and/or anti-oxidants can be utilized. In one embodiment, the deactivator comprises oxalyl bis(benzylidenehydrazide). Examples of suitable deactivators and/or anti-oxidants are commercially available from Eastman Chemical Co. of Kingsport, Tenn., such as Eastman™ OABH Inhibitor. While not required, the deactivator and/or anti-oxidant can be used in various amounts. In certain embodiments, the deactivator(s) is present in the composition in an amount of from about 0.01 to about 1, about 0.1 to about 0.75, about 0.1 to about 0.5, or about 0.1 to about 0.4, wt %, each based on the total weight of the composition.

In certain embodiments, the composition comprises a styrene dibromide. A specific example is 1,2 dibromoethyl benzene, which is commercially available from Sigma Aldrich. The styrene dibromide is useful for increasing thermal conductivity of the composition. In addition, the presence of a vinyl functional group allows the styrene to polymerize during formation of the conductor. While not required, the styrene dibromide can be used in various amounts. In certain embodiments, the styrene dibromide is present in the composition in an amount of from about 0.05 to about 1, about 0.1 to about 0.75, about 0.1 to about 0.5, or about 0.2 to about 0.3, wt %, each based on the total weight of the composition.

Referring now to the Figures, wherein like numerals indicate like parts throughout the several views, the composition is generally shown at 20″ and the conductor formed therefrom is generally shown at 20. As used herein, a quotation mark (″) generally indicates a different state of the respective component or composition, such as prior to curing, prior to sintering, etc., whereas lack of the ″ generally indicates a post or final cure state of the respective component or composition.

Referring to FIG. 1, the composition 20″ is disposed on a substrate 22 and is generally shown “pre-cured” on the left, and “cured” on the right such that it is the conductor 20. As alluded to above, the conductor 20 is useful for current transport and/or electrical connections for a variety of applications. The composition 20″ and conductor 20 is not limited to any particular application. The composition 20″ can be used to form various articles. Such articles generally include a substrate 22 with the conductor 20 disposed on the substrate 22. The substrate 22 can be formed from various materials. In one embodiment, the substrate 22 is also a conductor itself. Examples of such conductive substrates 22 include metals and semi-conductors. Specific examples of metal substrates 22 include aluminum, silver, or combinations thereof. Examples of semi-conductor substrates 22 include those formed from silicon, such as crystalline silicon. In other embodiments, the substrate 22 is a dielectric (or insulator). The composition 20″ can be disposed on a variety of materials, including combinations of those described above. Examples of other specific materials include both solderable and non-solderable metals, such as high melting point conductive metals, e.g. nickel or a conventional bulk substrate. In general, only metallic materials are considered to be solderable.

The conductor 20 can take various forms, and be of various sizes and shapes, such as being configured for use as a busbar, a contact pad, a fine line, a finger, and/or an electrode. For example, the composition 20″ can be used to form fine lines, e.g. 70 μm lines, dots, dots and lines, etc., by printing or other means. Other widths can also be formed. The conductor 20 is not limited to any particular shape or configuration. Some of the aforementioned components are useful for photovoltaic (PV) cells and other PV devices, which are described further below. The composition 20″ can be for other applications as well, such as for circuit boards, e.g. printed circuit board (PCB) production, or other applications requiring a conductive material. The conductor 20 is directly solderable, which provides improved connection means, such as by using tabbing to directly connect to the conductor 20. Said another way, typically there is no topcoat, protective, or outermost layer which needs to be removed from the conductor 20 prior to soldering directly thereto. This provides for reduced manufacturing time, complexity, and cost. For example, tabbing 52 can be directly soldered to the conductor 20 without the need for additional steps to be taken. In certain embodiments, an exception to this may be an additional fluxing step. In general, a surface is directly solderable if solder can be wet out on the surface after processing. For example, if one can either directly solder a wire to a substrate (within a commercially reasonable time frame and typically using an applied flux), use a tinned soldering iron to place a solder layer on the busbar, or simply heat up the substrate and see the solder wet out the electrode surface, the material would be directly solderable. In the case of a non-solderable system, even after applying flux and extensive heating, the solder never wets the surface, and no solder joint can be made.

In certain embodiments, the composition 20″ can be used as an adhesive by relying on its curing mechanism to form the conductor 20. For example, the composition 20″ can be applied and heated to form the conductor 20, and the conductor 20 can serve as an adhesive, such as holding a wire in place, holding two substrates together, etc. The wire can be disposed in the composition 20″ and/or the composition 20″ can be disposed on the wire, and subsequently cured to form the conductor 20, thereby holding the wire in place. Prior to final cure to form the conductor 20, the instant or intermediate adhesion strength provided by the composition 20″ may be referred to as green strength.

Further embodiments of various types of PV cells 32 utilizing the invention composition to form one or more structures/components thereof, such as busbars formed from the invention composition, are described in co-pending PCT Application No. ______ (Attorney Docket No. DC11371 PSP1; 071038.01087), and in co-pending PCT Application No. ______(Attorney Docket No. DC11372 PSP1; 071038.01089), both filed concurrently with the subject application, the disclosures of which are incorporated by reference in their entirety to the extent they do not conflict with the general scope of the present invention.

The present invention also provides a method of forming the conductor 20. The method includes the step of applying the composition 20″ to the substrate 22. The composition 20″ can be applied by various methods. Various types of deposition methods can be utilized, such as printing through screen or stencil, or other methods such as aerosol, ink jet, gravure, or flexographic, printing. In certain embodiments, the composition 20″ is screen printed directly onto the substrate 22. The composition 20″ is generally in the form of a paste, as such, printing is one method that can readily be utilized. As introduced above, solvent(s) can be utilized to adjust print viscosity of the composition 20″, if needed. The composition 20″ can be applied to the substrate 22 to make direct physical and electrical contact to the substrate 22.

As described above, the solder powder 24″ of the composition 20″ melts at lower temperature than melting temperature of the metal powder 26 of the composition 20″. The composition 20″ further comprises the polymers and other components 28″ described above. The method further comprises the step of heating the composition 20″ to a temperature of no greater than about 300° C. to form the conductor 20. The composition 20″ is generally heated to a temperature of from about 150 to about 300, about 175 to about 275, about 200 to about 250, about 200 to about 225, about 210 to about 225, or about 225, ° C. In certain embodiments, the composition 20″ is heated at about 250, about 225, or about 210, ° C. or less to form the conductor 20. In certain embodiments, the composition 20″ is heated to a temperature of from about 200 to about 300° C., or any temperature there between. These temperatures generally sinter the solder powder 24″, but do not sinter the metal powder 26, to form the conductor 20. Such heating may also be referred to in the art as reflow or sintering.

Referring to FIGS. 1 and 2, it is believed that the solder powder 24″ sinters and coats particles of the metal powder 26 during heating of the composition 20″ to form the conductor 20. Also during this time, the composition 20″ can lose volatiles and the polymers 28″ crosslink to a final cured state 28, generally providing adhesion to the substrate 22. As shown in FIG. 2, at least a portion of the polymer 28 is in direct contact with the substrate 22. An inter-metallic layer 30 generally forms around particles of the metal powder 26. Such coating enables the solder 24 coated particles of metal powder 26 to carry current, and can also prevent oxidation of metal powder 26. Due to the lower temperatures, the metal powder 26 does not generally sinter during the heating. The low temperature of this heating step generally allows for the use of temperature sensitive substrates 22, e.g. amorphous silicon or transparent conductive oxides.

The composition 20″ can be heated for various amounts of time to form the conductor 20. Typically, the composition 20″ is heated only for the period of time required for the conductor 20 to form. Such times can be determined via routine experimentation. An inert gas, e.g. a nitrogen (N₂) gas blanket, can be used to prevent premature oxidation of the metal powder 26 prior to being coated with the solder 24″. However, pre-fluxing of the metal powder 26 is generally not required. Unnecessarily overheating the conductor 20 for longer periods of time may damage the substrate 22 and/or the conductor 20.

Without being bound or limited by any particular theory, it is believed that the composition 20″ is generally self fluxing and oxidation resistant based on the following mechanism: heat onset activates the carboxylated-polymer to flux the solder and metal powders 24″,26. Released metallic oxides and salts, act as a catalyst and promote rapid cross linking between the polymer and the carboxylated-polymer at a higher temperature. The catalyzing oxides evolve from native metal, e.g. Cu, oxidation. The metallic salts are either produced from the reaction between the oxides and the carboxylated-polymer or are compounds used as lubricants/stability enhancers which have been released as a result of the solder and metal powders 24″,26 heating. In addition to the fluxing/cross-linking mechanisms, as the temperature increases, the solder powder 24″ melts and wets the particles of metal powder 26 and a sintering between the metal powder 26 and the solder powder 24 occurs as shown in FIG. 1 to form the inter-metallic layer 30. The solder coating 24 on the particles of the metal powder 26 is beneficial for preventing further oxidation of the metal powder 26 and maintaining conductivity of the conductor 20 over time.

Referring now to the FIGS. 3 through 11, a photovoltaic (PV) cell is generally shown at 32. As alluded to above, the composition 20″ can be used with PV cells 32. Specifically, the composition 20″ and resulting conductor 20 can be used with any type of PV cell, PV construct, or PV configuration. Said another way, the composition 20″ is not limited to any particular type of PV application. PV cells 32 are useful for converting light of many different wavelengths into electricity. As such, the PV cell 32 can be used for a variety of applications. For example, a plurality of PV cells 32 can be used in a solar module (not shown). The solar module can be used in a variety of locations and for a variety of applications, such as in residential, commercial, or industrial, applications. For example, the solar module can be used to generate electricity, which can be used to power electrical devices (e.g. lights and electric motors), or the solar module can be used to shield objects from sunlight (e.g. shield automobiles parked under solar modules that are disposed over parking spaces). The PV cell 32 is not limited to any particular type of use. The figures are not drawn to scale. As such, certain components of the PV cell 32 may be larger or smaller than as depicted.

Referring to FIG. 3, the PV cell 32 is shown in a square configuration with rounded corners, i.e., a pseudo-square. While this configuration is shown, the PV cell 32 may be configured into various shapes. For example, the PV cell 32 may be a rectangle with corners, a rectangle with rounded or curved corners, a circle, etc. The PV cell 32 is not limited to any particular shape. The PV cell 32 can be of various sizes, such as 4 by 4 inch (10.2 by 10.2 cm) squares, 5 by 5 inch (12.7 by 12.7 cm) squares, 6 by 6 inch (15.2 by 15.2 cm) squares, etc. The PV cell 32 is not limited to any particular size.

Referring to FIG. 4, the PV cell 32 comprises a base substrate 34. The base substrate 34 comprises silicon. The silicon may also be referred to in the art as a semiconductor material. Various types of silicon can be utilized, such as monocrystalline silicon, polycrystalline silicon, amorphous silicon, or combinations thereof. In certain embodiments, the base substrate 34 comprises crystalline silicon, e.g. monocrystalline silicon. The PV cell 32 is generally referred to in the art as a wafer type PV cell 32. Wafers are thin sheets of silicon that are typically formed from mechanically sawing the wafer from a single (mono) crystal or multicrystal silicon ingot. Alternatively, wafers can be formed from casting silicon, from epitaxial liftoff techniques, pulling a silicon sheet from a silicon melt, etc.

The base substrate 34 is generally planar, but may also be non-planar. The base substrate 34 can include a textured surface (not shown). The textured surface is useful for reducing reflectivity of the PV cell 32. The textured surface may be of various configurations, such as pyramidal, inverse pyramidal, random pyramidal, isotropic, etc. Texturing can be imparted to the base substrate 34 by various methods. For example, an etching solution can be used for texturing the base substrate 34. The PV cell 32 is not limited to any particular type of texturing process. The base substrate 34, e.g. wafer, can be of various thicknesses, such as from about 1 to about 1000, about 75 to about 750, about 75 to about 300, about 100 to about 300, or about 150 to about 200, μm thick on average.

The base substrate 34 is typically classified as a p-type or an n-type, silicon substrate (based on doping). In certain embodiments, the base substrate 34 includes an upper (or front side) doped region 36, which is generally the sun up/facing side. The upper doped region 36 may also be referred to in the art as a surface emitter, or active semiconductor, layer. In certain embodiments, the upper doped region 36 of the base substrate 34 is an n-type doped region 36 (i.e., an n⁺ emitter layer) such that a remainder of the base substrate 34 is generally p-type. In other embodiments, the upper doped region 36 of the base substrate 34 is a p-type doped region 36 (i.e., a p⁺ emitter layer) such that a remainder of the base substrate 34 is generally n-type. The upper doped region 36 can be of various thicknesses, such as from about 0.1 to about 5, about 0.3 to about 3, or about 0.4, μm thick on average. The upper doped region 36 may be applied such that doping under the fingers 44 (described below) is increased, such as in “selective emitter” technologies.

Referring to FIGS. 5 through 9, the base substrate 34 typically includes a rear doped region 38 opposite the upper doped region 36 (if present). The rear doped region 38 may also be referred to as a rear side doped region 38. In certain embodiments, the rear doped region 38 may also be referred to in the art as a back surface field (BSF). Typically, one of the doped regions, e.g. the upper 36, is an n-type and the other doped region, e.g. the rear 38, is a p-type. The opposite arrangement may also be used, i.e., the upper 36 is a p-type and the rear 38, is an n-type. Such configurations, where the oppositely doped region 36,38 interfaces, are referred to in the art as p-n junctions (J) and are useful for photo-excited charge separation provided there is at least one positive (p) region and one negative (n) region. Specifically, when two regions of different doping are adjacent, a boundary defined there between is generally referred to in the art as a junction. When the doping are of opposite polarities then the junction (J) is generally referred to as a p-n junction (J). When doping is merely of different concentrations, the “boundary” may be referred to as an interface, such as an interface between like regions, e.g. p and p⁺ regions. As shown generally in the Figures, such junctions (J) may be optional, depending on what type of doping is utilized in the base substrate 34. The PV cell 32 is not limited to any particular number or location of junction(s) (J). For example, the PV cell 32 may only include one junction (J), such as on the front or rear.

Referring to FIGS. 5 through 8, the base substrate 34 includes an n-type or p-type rear doped region 38. Referring to FIG. 9, the base substrate 34 includes localized doped regions 38. In certain embodiments, the localized doped regions 38 are n-type; while in other embodiments, the regions 38 are p-type.

Various types of dopants and doping methods can be utilized to form the doped regions 36,38 of the base substrate 34. For example, a diffusion furnace can be used to form an n-type doped region 36,38 and a resulting n-p (or “p-n”) junction (J). An example of a suitable gas is phosphoryl chloride (POCl₃). In addition or alternate to phosphorus, arsenic can also be used to form n-type regions 36,38. At least one of the periodic table elements from group V, e.g. boron or gallium, can be used to form p-type regions 36,38. The PV cell 32 is not limited to any particular type of dopant or doping process.

Doping of the base substrate 34 can be at various concentrations. For example, the base substrate 34 can be doped at different dopant concentrations to achieve resistivity of from about 0.5 to about 10, about 0.75 to about 3, or about 1, Ω·cm (Ω·cm). The upper doped region 36 can be doped at different dopant concentrations to achieve sheet resistivity of from about 50 to about 150, or about 75 to about 125, or about 100, Ω/□(Ω per square). In general, a higher concentration of doping may lead to a higher open-circuit voltage (V_OC) and lower resistance, but higher concentrations of doping can also result in charge recombination depleting cell performance and introduce defect regions in the crystal.

Typically, there is a first electrode 40 disposed on the rear doped region 38, opposite the upper doped region 36 (if present). The first electrode 40 has an outer surface 41. The first electrode 40 may cover the entire rear doped region 38 or only a portion thereof. If the later, typically a passivation layer 42, e.g. a layer of SiN_x, is used to protect exposed portions of the rear doped region 38, but the passivation layer 42 is not used between the first electrode 40 and the portion of rear doped region 38 in direct physical and electrical contact. The first electrode 40 may take the form of a layer, a layer having localized contacts, or a contact grid comprising fingers and busbars. Examples of suitable configurations include, but are not limited to, p-type base configurations, n-type base configurations, PERC or PERL type configurations, bifacial BSF type configurations, heterojunction with intrinsic thin layer (HIT) configurations, emitter wrap through (EWT) configurations, metal wrap through (MWT) configurations, interdigitated back contact (IBC) configurations, etc. The PV cell 32 is not limited to any particular type of first electrode 40 or electrode configuration.

The first electrode 40 may take the form of a layer (e.g. FIGS. 5 and 6), a layer having localized contacts (e.g. FIGS. 8 and 9), or a contact grid comprising fingers, dots, pads, and/or busbars (e.g. FIG. 7). Examples of suitable configurations include p-type base configurations, n-type base configurations, PERC or PERL type configurations, bifacial BSF type configurations, heterojunction with intrinsic thin layer (HIT) configurations, etc. The PV cell 32 is not limited to any particular type of electrode 40 or electrode configuration. The first electrode 40 can be of various thicknesses, such as from about 0.1 to about 500, about 1 to about 100, or from about 5 to about 50, μm thick on average. Some of these embodiments, as well as others, are described in detail below.

In certain embodiments, the first electrode 40 comprises a first metal, which is present in (each of) the first electrode(s) 40 in a majority amount. The first metal may comprise various types of metals. In certain embodiments, the first metal comprises Al. In other embodiments, the first metal comprises Ag. In yet other embodiments, the first metal comprises a combination of Ag and Al. By “majority amount”, it is generally meant that the first metal is the primary component of the first electrode 40, such that it is present in an amount greater than any other component that may also be present in the first electrode 40. In certain embodiments, such a majority amount of the first metal, e.g. Al and/or Ag, is generally greater than about 35, greater than about 45, or greater than about 50, wt %, each based on the total weight of the first electrode 40.

In embodiments where the rear doped region 38 is a p-type, the first electrode 40 typically comprises at least one of the periodic table elements of group III, e.g. aluminum (Al). Al can be used as a p-type dopant. For example, an Al paste can be applied to the base substrate 34 and then fired to form the first electrode 40, while also forming the rear p⁺-type doped region 38. The Al paste can be applied by various methods, such as by a screen printing process. Other suitable methods are described below.

As best shown in FIG. 6, a second electrode 45 is spaced from the rear doped region 38 of the base substrate 34. The rear doped region 38 is free of (direct) physical contact with the second electrode 45. The second electrode 45 is in electrical contact with the first electrode 40. The second electrode 45 need only contact a portion of the first electrode 40, or it can cover an entirety of the first electrode 40. The first and second electrodes 40,45 may be referred to in the art as an electrode stack. The rear doped region 38 is in electrical communication with the second electrode 45 via the first electrode 40. The second electrode 45 is typically configured in the shape of a pad(s) 45, contact pad(s) 45, or busbar(s) 45. Reference to the second electrode 45 herein can refer to various configurations.

For example, as best shown in FIGS. 10 and 11, the PV cell 32 can include a pair of second electrodes 45, shaped as busbars 45, on the first electrode 40. In addition, a pair of front busbars 50 is disposed opposite the second electrodes 45 in generally a mirror configuration. The second electrodes 45 and the busbars 50 can be the same or different from each other, both in chemical makeup and/or in physical characteristic, such as shape and size. The busbars 50 are described further below.

As shown in FIGS. 5, 10 and 11, the PV cell 32 can have two second electrodes 45. In certain embodiments, the PV cell 20 may have more than two second electrodes 45, such as three second electrodes 45, four second electrodes 45, six second electrodes 45, etc. Each second electrode 45 is in electrical contact with at least one electrode 40. The second electrodes 45 are useful for collecting current from the first electrode 40 which has collected current from the rear doped region 38. As shown generally, the second electrode 45 is disposed directly on the outer surface 41 of the first electrode 40 to provide intimate physical and electrical contact thereto. This places the second electrode 45 in position for carrying current directly from the first electrode 40. The first electrode 40 is in intimate physical and electrical contact with the rear doped region 38 of the base substrate 34.

The second electrode 45 can be of various widths, such as from about 0.5 to about 10, about 1 to about 5, or about 2, mm wide on average. The second electrode 45 can be of various thicknesses, such as from about 0.1 to about 500, about 10 to about 250, about 30 to about 100, or about 30 to about 50, μm thick on average. The second electrode 45 can be spaced various distances apart.

The second electrode 45 can be formed from various materials. In one embodiment, the second electrode 45 is formed from the invention composition 20″, i.e., the conductor 20 is the second electrode 45. In other embodiments, the second electrode 45 is formed similar to or like to the busbars 50. The second electrode 45 can be formed in the same manner(s) as described below for the busbars 50.

As best shown in FIGS. 4, 5, 10, and 11, the passivation layer 42 is disposed on the upper doped region 36. The passivation layer 42 is useful for increasing sunlight absorption by the PV cell 32, e.g. by reducing reflectivity of the PV cell 32, as well as generally improving wafer lifetime through surface and bulk passivation. The passivation layer 42 has an outer surface 43 opposite the upper doped region 36. The passivation layer 42 may also be referred to in the art as a dielectric passivation, or anti-reflective coating (ARC), layer.

The passivation layer 42 may be formed from various materials. In certain embodiments, the passivation layer 42 comprises SiO_x, ZnS, MgF_x, SiN_x, SiCN_x, AlO_x, TiO₂, a transparent conducting oxide (TCO), or combinations thereof. Examples of suitable TCOs include doped metal oxides, such as tin-doped indium oxide (ITO), aluminum-doped zinc-oxide (AZO), indium-doped cadmium-oxide, fluorine-doped tin oxide (FTO), or combinations thereof. In certain embodiments, the passivation layer 42 comprises SiN_x. Employing SiN_xis useful due to its excellent surface passivation qualities. Silicon nitride is also useful for preventing carrier recombination at the surface of the PV cell 32.

The passivation layer 42 may be formed from two or more sub-layers (not shown), such that the passivation layer 42 may also be referred to as a stack. Such sub-layers can include a bottom ARC (B-ARC) layer and/or a top ARC (T-ARC) layer. Such sub-layers can also be referred to as dielectric layers, and be formed from the same or different material. For example, there may be two or more sub-layers of SiN_x; a sub-layer of SiN_xand a sub-layer of AlO_x; etc.

The passivation layer 42 can be formed by various methods. For example, the passivation layer 42 can be formed by using a plasma-enhanced chemical vapor deposition (PECVD) process. In embodiments where the passivation layer 42 comprises SiN_x, silane, ammonia, and/or other precursors can be used in a PECVD furnace to form the passivation layer 42. The passivation layer 42 can be of various thicknesses, such as from about 10 to about 150, about 50 to about 90, or about 70, nm thick on average. Sufficient thickness can be determined by the refractive indices of the coating material and base substrate 34. The PV cell 32 is not limited to any particular type of coating process.

In certain embodiments, a plurality of fingers 44 are spaced from each other and disposed in the passivation layer 42. Each of the fingers 44 has a lower portion 46 in electrical contact with the upper doped region 36 of the base substrate 34. The lower portion 46 in actual electrical contact may be quite small, such as tips/ends of the fingers 44. Each of the fingers 44 also has an upper portion 48 opposite the lower portion 46 extending outwardly through the outer surface 36 of the passivation layer 42. The fingers 44 are generally disposed in a grid pattern, as best shown in FIGS. 1 and 4. Typically, the fingers 44 are disposed such that the fingers 44 are relatively narrow while being thick enough to minimize resistive losses. Orientation and number of the fingers 44 may vary.

The fingers 44 can be of various widths, such as from about 10 to about 200, about 70 to about 150, about 90 to about 120, or about 100, μm wide on average. The fingers 44 can be spaced various distances apart from each other, such as from about 1 to about 5, about 2 to about 4, or about 2.5, mm apart on average. The fingers 44 can be of various thicknesses, such as from about 5 to about 50, about 5 to about 25, or about 10 to about 20, μm thick on average.

In certain embodiments, one of more of the fingers 44 are formed from the invention composition 20″, i.e., the conductors 20 are the fingers 44. In other embodiments, each of the fingers 44 comprises a first metal, which is present in each of the fingers 44 in a majority amount. The first metal may comprise various types of metals. In certain embodiments, the first metal comprises silver (Ag). In other embodiments, the first metal comprises copper (Cu). By “majority amount”, it is generally meant that the first metal is the primary component of the fingers 44, such that it is present in an amount greater than any other component that may also be present in the fingers 44. In certain embodiments, such a majority amount of the first metal, e.g. Ag, is generally greater than about 35, greater than about 45, or greater than about 50, wt %, each based on the total weight of the finger 44.

The fingers 44 can be formed by various methods. Suitable methods include sputtering; vapor deposition; strip or patch coating; ink-jet printing, screen printing, gravure printing, letter printing, thermal printing, dispensing or transfer printing; stamping; electroplating; electroless plating; or combinations thereof. Such methods can also be used to form the conductor 20 from the composition 20″. One type of method is generally referred to as an etching/firing process. In addition to the invention composition 20″, other compositions for forming the fingers 44 are described further below.

In certain embodiments, the fingers 44 are formed by a plating process (rather than an etching/firing process). In these embodiments, the fingers 44 generally comprise a plated or stacked structure (not shown). For example, the fingers 44 can comprise two or more of the following layers: nickel (Ni), Ag, Cu, and/or Sn. The layers can be in various orders, provided the Cu layer (if present) is not in direct physical contact with the upper doped region 36 of the base substrate 34. Typically, a seed layer comprising Ag or a metal other than Cu, e.g. Ni, is in contact with the upper doped region 36. In certain embodiments, the seed layer comprises Ni silicide. Subsequent layers are then disposed on the seed layer to form the fingers 44. When the fingers 44 include Cu, a passivation layer such as Sn or Ag is disposed over the Cu layer to prevent oxidation. In certain embodiments, the lower portions 46 of the fingers 44 comprise Ni, the upper portions 48 of the fingers 44 comprise Sn, and Cu is disposed between the Ni and Sn. In this way, the Cu is protected from oxidation by the Ni, Sn, and surrounding passivation layer 42. Such layers can be formed by various methods, such as aerosol printing and firing; electrochemical deposition; etc. The PV cell 32 is not limited to any particular type of process of forming the fingers 44.

A busbar 50 is spaced from the upper doped region 36 of the base substrate 34. As shown in FIGS. 3, 10, and 11, the PV cell 32 generally has two busbars 50. In certain embodiments, the PV cell 32 may have more than two busbars 50 (not shown), such as three busbars 50, four busbars 50, six busbars 50, etc. Each busbar 50 is in electrical contact with the upper portions 48 of the fingers 44. The busbars 50 are useful for collecting current from the fingers 44 which have collected current from the upper doped region 36. As best shown in FIG. 10, each of the busbars 50 is disposed on the outer surface 34 of the passivation layer 42 and around each of the fingers 44 to provide intimate physical and electrical contact to the upper portions 48 of the fingers 44. Typically, the busbar 50 is transverse the fingers 44. Said another way, the busbar 50 can be at various angles relative to the fingers 44, including perpendicular. The upper portion 48 in actual physical/electrical contact may be small, such as just tips/ends of the fingers 44. Such contact places the busbar 50 in position for carrying current directly from the fingers 44. The fingers 44 themselves are in intimate physical and electrical contact with the upper doped region 36 of the base substrate 34. Typically, only one junction (J) is present in the PV cell 32 of FIG. 10, such as in the front or rear of the base substrate 34.

The busbar 50 can be of various widths, such as from about 0.5 to about 10, about 1 to about 5, or about 2, mm wide on average. The busbar 50 can be of various thicknesses, such as from about 0.1 to about 500, about 10 to about 250, about 30 to about 100 or about 30 to about 50, μm thick on average. The busbars 50 can be spaced various distances apart. Typically, the busbars 50 are spaced to divide lengths of the fingers 44 into ˜equal regions, e.g. as shown in FIG. 1.

In certain embodiments, one of more of the busbars 50 is/are formed from the invention composition 20″, i.e., the conductors 20 are the busbars 50. In other embodiments, the busbar 50 comprises a second metal, which is present in the busbar 50 in a majority amount. The “second” is used to differentiate the metal of the busbar 50 from the “first” metal of the fingers 44, and does not imply quantity or order. The second metal may comprise various types of metals. In certain embodiments, the second metal of the busbar 50 is the same as the first metal of the fingers 44. For example, both the first and second metals can be Cu. In other embodiments, the second metal of the busbar 50 is different from the first metal of the fingers 44. In these embodiments, the first metal typically comprises Ag and the second metal typically comprises Cu. In other embodiments, the second metal comprises Ag. By “majority amount”, it is generally meant that the second metal is the primary component of the busbar 50, such that it is present in an amount greater than any other component that may also be present in the busbar 50. In certain embodiments, such a majority amount of the second metal, e.g. Cu, is generally greater than about 25, greater than about 30, greater than about 35, or greater than about 40, wt %, each based on the total weight of the busbar 50.

The busbar 50 also generally comprises a third metal. The third metal is different from the first metal of the fingers 44. The third metal is also different from the second metal of the busbar 50. Typically, the metals are different elements, rather than just different oxidation states of the same metal. The “third” is used to differentiate the metal of the busbar 50 from the “first” metal of the fingers 44, and does not imply quantity or order. The third metal melts at a lower temperature than melting temperatures of the first and second metals. Typically, the third metal has a melting temperature of no greater than about 300, no greater than about 275, or no greater than about 250, ° C. Such temperatures are useful for forming the busbar 50 at low temperatures as described further below.

In certain embodiments, the third metal comprises solder, which may be the same or different from the solder of the composition 20″. The solder can comprise various metals or alloys thereof. One of these metals is typically Sn, lead, bismuth, cadmium, zinc, gallium, indium, tellurium, mercury, thallium, antimony, selenium and/or an alloy of two or more of these metals. The third metal can be present in the busbar 50 in various amounts, typically in an amount less than the second metal. The busbar 50 typically comprises a polymer(s) in addition to the second and third metals, as described further below, which may be the same or different than the polymers of the composition 20″.

As best shown in FIG. 10, the upper doped region 36 of the base substrate 34 is free of (direct) physical contact with the busbar 50. Specifically, the passivation layer 42 serves as a “barrier” between the busbar 50 and upper doped region 36. Without being bound or limited by any particular theory, it is believed that physical separation of the busbar 50 and the upper doped region 36 is beneficial for at least two reasons. First, such separation prevents diffusion of the second metal, e.g. Cu, into the base substrate 34. It is believed that preventing such diffusion prevents the opposite doped region from being shunted by the second metal of the busbar 50. Second, such physical separation is believed to reduce minority carrier recombination at the metal and silicon interfaces. It is believed that by reducing the area of metal/silicon interface, loss due to recombination is generally reduced and open-circuit voltage (V_OC) and short-circuit current density (J_SC) are generally improved. The area is reduced due to the passivation layer 42 being disposed between much of the busbar 50 and the upper doped region 36, with the fingers 44 being the only metal components in contact with the upper doped region 36 of the base substrate 34. Additional embodiments of the PV cell 32 will now be described immediately below.

The PV cell 32 of FIG. 12 is similar to that of FIG. 3A, but includes discontinuous-fingers 44. The busbar 50 is disposed over a gap 47 defined between the fingers 44. The gap 47 can be of various widths, provided the busbar 50 is in electrical contact with the fingers 44. The fingers 44 may comprise a majority of one metal, e.g. Ag, whereas the busbar 50 another metal, e.g. Cu (as like described above). By having gaps 47, cost of manufacture can be reduced (such as by reducing the total amount of Ag utilized), and/or adhesion may be positively impacted.

The PV cell 32 of FIG. 13 is similar to that of FIG. 12, but further includes supplemental fingers 44b disposed over the fingers 44a. The supplemental fingers 44b may comprise the same material as the busbar 50, e.g. Cu, or a different material. The supplemental fingers 44b and the busbar 50 may be separate (e.g. one lying over the other) or unitary. By utilizing the supplemental fingers 44b, the size of the fingers 44a (e.g. Ag fingers) can be reduced, which can reduce cost of manufacture and/or improve adhesion.

The PV cell 32 of FIG. 14 includes fingers 44, busbar 50a, and supplemental busbar pads 50b disposed over the fingers 44 and busbar 50a. The fingers 44 and busbar 50 may be separate or unitary. The fingers 44 and busbar 50a may comprise the same majority metal, e.g. Ag, or be different than each other. The busbar pads 50b can comprise Cu or another metal, e.g. when formed from the invention composition. By utilizing the busbar pads 50b, the size of the busbar 50a (e.g. Ag busbar 50a) can be reduced.

The PV cell 32 of FIG. 15 is similar to that of FIGS. 12 and 14, but includes a pair of busbars 50a and a supplemental busbar 50b disposed over the busbars 50a. The fingers 44 and busbars 50a can be separate or unitary. The fingers 44 and busbar 50a may comprise the same majority metal, e.g. Ag, or be different than each other. The supplemental busbar 50b can comprise Cu or another metal. By utilizing the supplemental busbar 50b, the size of the busbars 50a can be reduced.

The PV cells 32 of FIGS. 16 and 17 are similar to that of FIG. 12, but include fingers 44 having pads in place of the gaps 47. The padded fingers 44 can help to improve electrical contact to the busbar 50, and adhesion, while reducing the amount of Ag used and reducing manufacturing cost. The fingers 44 of FIG. 17 have hollow pads, i.e., internal gaps 47, which can reduce cost of manufacture and positively impact adhesion. A portion of the busbar 50 may be disposed in the gaps 47 of the hollow padded fingers 44.

The PV cell 32 of FIG. 18 is similar to that of FIG. 12, but includes discontinuous-fingers 44a with supplemental fingers 44b disposed thereon. The discontinuous-fingers 44a can be in various shapes, such as rectangles, squares, dots, or combinations thereof. Such fingers 44a can be plated, printed, or formed in another manner. A plurality of gaps 47 are defined by the discontinuous-fingers 44a. The supplemental fingers 44b and the busbar 50 may be separate or unitary. By utilizing the discontinuous-fingers 44a and supplemental fingers 44b, cost of manufacture can be reduced. The discontinuous-fingers 44a typically contact the emitter 26 while the supplemental fingers 44b and busbar 50 carry current.

The PV cells 32 of FIGS. 19 and 20 are similar to that of FIG. 3B. In FIG. 19, the first electrode 40 defines a hole 49, whereas in FIG. 20, the first electrode 40 defines a plurality of holes 49. The hole(s) 49 is/are also defined by the passivation layer 42, if present. The second electrode 45 is disposed over the first electrode 40 and is in electrical contact with the base substrate 34 via the hole(s) 49. The base substrate 34 may or may not include doping 38 proximal the hole(s) 49. The base substrate 34 can be in direct contact with the second electrode 45. When the second electrode 45 is formed from the composition 20″, the solder 24 can prevent the possibility of the metal powder 26, e.g. Cu, leaching/migrating into the base substrate 34, e.g. Si. By utilizing the holes 49, cost of manufacture can be reduced. Alternatively, a dielectric passivation layer 42 may be between the Cu electrode 45 and the substrate 34. A possible benefit of a passivation layer 42 is an improved reduction in charge recombination resulting in improved cell 32 efficiency.

The PV cell 32 of FIG. 21 is of an interdigitated back contact (IBC) configuration, with interdigitated fingers 40, and a pair of busbars 45. The busbars 45 can be formed from the composition 20″, whereas the fingers 40 can be formed from another material, e.g. Ag. Such IBC configurations are understood in the art. The composition 20 is not limited to any particular type of configuration as described above.

The present invention also provides a method of forming the PV cell 32. The method includes the step of applying the composition 20″ to the upper portions 48 of the fingers 44 to form a layer 50″. The composition can be applied by various methods, as alluded to above. In certain embodiments, the composition is printed on at least a portion of the upper portions 48 of the fingers 44 to form a layer 50″. Various types of deposition methods can be utilized, such as printing through screen or stencil, or other methods such as aerosol, ink jet, gravure, or flexographic, printing. In certain embodiments, the composition is screen printed directly onto portions of the passivation layer 42 and the upper portions 48 of the fingers 44.

After application of the composition 20″, the upper doped region 36 of the base substrate 34 is typically free of (direct) physical contact with the layer 50″. The composition 20″ can be applied to the passivation layer 42 and around each of the fingers 44 to make direct physical and electrical contact to the upper portions 48 of the fingers 44 with the layer 50″.

The method further comprises the step of heating the layer 50″ to a temperature of no greater than about 300° C. to form the busbar 50 (i.e., the conductor 20). The layer 50″ is generally heated to a temperature of from about 150 to about 300, about 175 to about 275, about 200 to about 250, or about 225, ° C. In certain embodiments, the layer 50″ is heated at about 250° C. or less to form the busbar 50. Such temperatures generally sinter the third metal (i.e., solder powder) in the layer 50″, but do not sinter the second metal (e.g. the metal powder) in the layer 50″ to form the busbar 50. Such heating may also be referred to in the art as reflow or sintering.

The layer 50″ can be heated for various amounts of time to form the busbar 50. Typically, the layer 50″ is heated only for the period of time required for the busbar 50 to form. Such times can be determined via routine experimentation. An inert gas, e.g. a N₂gas blanket, can be used to prevent premature oxidation of the Cu 26 prior to being coated with the solder 24″. Unnecessarily overheating the busbar 50 for longer periods of time may damage the upper doped region 36 or other components of the PV cell 32 including the busbar 50. The same type of method can be utilized to form the second electrode 45 on the first electrode 40 using the invention composition. This can be alternate to, or in addition to, forming the busbars 50 with the invention composition 20″ as described above.

In one embodiment, prior to forming the busbar 50, the method comprises the step of applying a coating composition to the upper doped region 36 of the base substrate 34 to form the passivation layer 42. The coating composition can comprise various components, such as those suitable for forming the passivation layers 42 described above. The coating composition can be applied by various methods, as introduced above. For example, a PECVD process can be utilized. In embodiments where the passivation layer 42 comprises SiN_x, silane, ammonia, and/or other precursors can be used in a PECVD furnace to form the passivation layer 42.

The method further comprises the step of applying a metallic composition to portions of the passivation layer 42 in a finger pattern corresponding to the fingers 44 to be formed. Each of the finger patterns generally has their lower portion in contact with the passivation layer 42 and their upper portion spaced from the passivation layer 42 after application. The metallic composition can be applied by various methods, as alluded to above. In certain embodiments, the metallic composition is printed on portions of the passivation layer 42 to form the finger patterns. Various types of printing methods can be utilized, such as screen, stencil, aerosol, ink jet, gravure, or flexographic, printing. In certain embodiments, the metallic composition is screen printed directly onto the passivation layer 42 to form the finger patterns. In other embodiments, the metallic composition is electrochemically deposited on portions of the passivation layer 42 to form the finger patterns. Other suitable methods are described above.

The metallic composition comprises the first metal present in the metallic composition in a majority amount. Such amounts are as described above. Typically, the first metal is Ag. The metallic composition typically includes one or more components for etching into the passivation layer 42. Such components generally include fritted leaded glass. Other components may also be used in addition or alternate to leaded glass, such as unleaded or low leaded glass.

Various types of fritted or unfritted Ag of Al pastes can be used as the metallic composition. Such pastes generally include an organic carrier. Upon high temperature processing or “firing”, the organic carrier burns out and is removed from the bulk composition. Ag particles are dispersed throughout the carrier. A solvent may be included to adjust rheology of the paste. The fritted paste includes glass frits, which generally comprises PbO, B₂O₃, and SiO₂. The method is not limited to any particular fritted Ag paste, provided the paste can etch through the cover sheet at elevated temperatures, as described below. Examples of suitable fritted Ag pastes are commercially available from Ferro of Mayfield Heights, Ohio and Heraeus Materials Technology, LLC of West Conshohocken, Pa.

The method further comprises the step of heating the finger patterns to form the fingers 44. The finger patterns are generally heated to a temperature of from about 250 to about 1000, from about 500 to about 900, or about 720, ° C. Such temperatures generally sinter the first metal in the finger patterns to form the fingers 44. This heating step is generally much higher in temperature relative to the heating step used to form the busbar 50 (i.e., conductor 20). In addition, the glass frit allows for the finger patterns to etch through the passivation layer 42 and upon cooling, phase separate. This allows for direct electrical contact of the fingers 44 to the upper doped region 36 of the base substrate 34. Such heating may also be referred to in the art as firing.

The finger patterns can be heated for various amounts of time to etch through the passivation layer 42. Typically, the finger patterns are heated only for the period of time required for the fingers 44 to uniformly contact the upper doped region 36. Such times can be determined via routine experimentation. Unnecessarily overheating the fingers 44 for longer periods of time may damage the upper doped region 36 or other components of the PV cell 32. After heating the finger patterns such that they can etch through the passivation layer 42, the method further comprises the step of applying a composition to at least a portion of the upper portions 48 of the fingers 44 to form the layer 50″ as described above.

In another embodiment, the fingers 44 are formed in a different manner than as described in the embodiment above. The passivation layer 42 can be formed as described above. After forming the passivation layer 42, holes are formed therein. The holes can be formed by various methods, such as by laser ablation, chemical etching, physical etching, etc. Such etching is different from the finger 36 “etching” described above. The fingers 44 are then formed in the holes. These fingers 44 are generally the plated fingers 44 as described above. The fingers 44 can be formed by depositing various metals into the holes. Various processes can be used, and different processes can be used for each layer of the fingers 44. An electrochemical plating process may be used to form the layers in the holes. Typically, such processes do not require a separate heating/firing step as described above. After forming the fingers 44, the method further comprises the step of applying a composition to at least a portion of the upper portions 48 of the fingers 44 to form the layer 50″ as described above.

As like the conductor 20, the busbar 50 is directly solderable, which is useful for tabbing multiple PV cells 32 together, such as by attaching ribbons or interconnects to the busbars 50 of the PV cells 32. By using the busbar 50 and tabbing, it is possible to collect current from the fingers 44 effectively. As introduced above, the PV cell 32 may be used in various applications.

Referring to FIG. 11, tabbing 52 is disposed on the busbars 50. In certain embodiments, the tabbing 52 is directly solderable to the busbars 50 of the PV cells 32. In other embodiments, additional solder (not shown) may be used between the busbars 50 and tabbing 52. Fluxing means may be used to aid in soldering, such a flux pen or flux bed. The tabbing 52 itself may also include flux, such as Sn or Sn alloys and flux. The tabbing 52 can be formed from various materials, such as Cu, Sn, etc. Such tabbing 52 can be used to connect a series of PV cells 32. For example, a PV cell module (not shown) can include a plurality of the PV cells 32. Tabbing 52, e.g. ribbon, is generally in physical contact with the busbars 50 of the PV cells 32 to electrically connect the PV cells 32 in series. The tabbing 52 may also be referred to in the art as an interconnection. The PV module may also include other components, such as tie layers, substrates, superstrates, and/or additional materials that provide strength and stability. In many applications, the PV cells 32 are encapsulated to provide additional protection from environmental factors such as wind and rain.

The following examples, illustrating the composition 20″ and conductors 20 of the present invention are intended to illustrate and not to limit the invention. The amount and type of each component used to form the compositions is indicated in Tables 1 through 3 below with all values in wt % based on a total weight of the respective composition unless otherwise indicated.

TABLE 1

Component
Example

(wt %)
0
1
2

Polymer
1.7601
1.7325
1.7243

Additive 1
2.0467
2.0145
2.0050

Additive 2
0.2865
0.2820
0.2807

Carboxylated-Polymer
3.7208
3.6627
3.6362

Dicarboxylic Acid
0.2489
0.4875
0.2432

Monocarboxylic Acid
0.4953
0.2450
0.4840

Additive 3
1.8608
1.8317
1.8185

Additive 4
1.8608
1.8317
1.8185

Metal Powder
47.7200
46.9642
46.5600

Solder Powder 1
15.6250
15.6520
16.2283

Solder Powder 2
24.3750
23.8343
23.7501

Additive 5
—
0.2931
0.5567

Additive 6
—
0.1016
—

Additive 7
—
0.1718
—

Additive 8
—
0.2715
0.3036

Additive 9
—
0.6239
0.5907

Total
100.00
100.00
100.00

Polymer is a solid epoxy resin comprising the reaction product of epichlorohydrin and bisphenol A and having an EEW of 500-560 g/eq, commercially available from Dow Chemical.

Additive 1 is a monoterpene alcohol, commercially available from Sigma Aldrich.

Additive 2 is a styrene dibromide, commercially available from Sigma Aldrich.

Carboxylated-Polymer is a low molecular weight styrene-acrylic copolymer having an acid value of about 238 (on solids), commercially available from BASF Corp.

Dicarboxylic Acid is commercially available from Sigma Aldrich.

Monocarboxylic Acid is commercially available from Hexion Specialty Chemicals.

Additive 3 is a propylene glycol, commercially available from Sigma Aldrich.

Additive 4 is a benzyl alcohol, commercially available from Sigma Aldrich.

Metal Powder is copper powder, commercially available from Mitsui Mining & Smelting Co.

Solder Powder 1 is a Sn42/Bi58 alloy, having a melting temperature of about 138° C., commercially available from Indium Corporation of America.

Solder Powder 2 is a Sn96.5/Ag3.5 alloy, having a melting temperature of about 221° C., commercially available from Indium Corporation of America.

Additive 5 is a titanate adhesion promoter, commercially available from Kenrich Petrochemicals Co.

Additive 6 is a copper deactivator comprising oxalyl bis(benzylidenehydrazide), commercially available from Eastman Chemical Co.

Additive 7 is a silicone-free defoamer, commercially available from BYK additives & instruments.

Additive 8 is a silane adhesion promoter comprising 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, commercially available from Dow Corning Corp.

Additive 9 is a butyl carbitol, commercially available from Dow Chemical.

TABLE 2

Component
Example

(wt %)
3
4
5

Polymer
1.7051
1.6997
1.7467

Additive 1
1.9827
1.9765
2.0311

Additive 2
0.2776
0.2767
0.2844

Carboxylated-Polymer
3.6036
3.5941
3.6952

Dicarboxylic Acid
0.2410
0.2404
0.2472

Monocarboxylic Acid
0.4797
0.4784
0.4919

Additive 3
1.8022
1.7974
1.8480

Additive 4
1.8022
1.7974
1.8480

Metal Powder
46.1663
46.0697
57.8686

Solder Powder 1
17.2656
17.3370
16.1390

Solder Powder 2
23.4148
23.3854
12.8472

Additive 5
—
—
0.3184

Additive 6
0.3258
—
0.1570

Additive 7
—
0.3084
0.1259

Additive 8
0.2581
0.3498
0.2681

Additive 9
0.6752
0.6891
0.0834

Total
100.00
100.00
100.00

TABLE 3

Component
Example

(wt %)
6
7
8
9

Polymer
1.7451
1.7873
4.9492
4.9664

Additive 1
2.0241
1.5386
4.2386
4.2533

Additive 2
0.3049
0.3021
0.6893
0.6917

Carboxylated-Polymer
—
5.1469
2.4731
2.4430

Dicarboxylic Acid
—
—
1.9982
1.9738

Monocarboxylic Acid
—
—
—
—

Additive 3
1.8593
—
2.4778
2.4476

Additive 4
1.8849
5.4753
—
—

Metal Powder
47.2075
56.4608
29.7952
39.3662

Solder Powder 1
15.4282
14.0947
10.8638
13.6477

Solder Powder 2
24.0367
14.3246
31.8660
29.4230

Silver Powder 1
—
—
9.8041
—

Dimer Acid
4.4656
—
—
—

Additive 5
0.4775
0.3589
0.5798
0.5230

Additive 6
0.1817
0.1157
—
—

Additive 7
0.1288
0.1370
0.2647
0.2642

Additive 8
0.1111
0.1440
—
—

Additive 9
—
—
—
—

Additive 10
0.1446
0.1142
—
—

Total
100.00
100.00
100.00
100.00

Silver powder is a conventional silver flake from Ferro.

Dimer Acid is a distilled dimerized fatty acid with low monomer content and trimer content, commercially available from Arizona Chemical of Jacksonville, Fla.

Additive 10 is 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Referring to FIGS. 22 and 23, data from 90 degree peel testing illustrates paste adherence to different substrates and paste capability to connect to external wiring through soldering. Referring to FIG. 24, paste bulk resistance dependence on the difference in composition is illustrated. It is evident that the resistivity of all nine pastes which slightly differ in composition and main components ratios remains relatively unaffected and is in the range of 3 to 6×10⁻⁵Ω·cm. Example numbers of Tables 1 through 3 correspond to those numbers in FIGS. 22 through 24, i.e. Examples 1 through 9.

A series of 5 inch (12.7 cm) monocrystalline silicon cells (wafers) are prepared for application of Ag and Cu pastes. Cu paste based on Example 0 in Table 1 above is prepared The Cu paste is diluted down with 1 wt % butyl carbitol to improve print rheology. The Cu paste is printed on the wafers to form Cu busbars via a busbar screen from Sefar, a stainless steel screen 325 or 165 mesh, with a 12.7 μm emulsion thickness (PEF2), and a 22° or 45° rotation of the mesh. Printing is performed with an AMI screen printer with a ˜0.68 kg down force, with a 200 μm blank wafer on the stage. Print speed is set to between 3 to 5 inch/sec in a print-print mode. The wafers are printed and put through a BTU Pyramax N₂reflow oven.

Durability of the Cu busbars under damp heat (DH; 85° C., 85% relative humidity) aging conditions is determined. Unencapsulated prints of Cu busbars on silicon are used to monitor the Cu bulk resistivity (ρ). The quality of the tabbing/Cu busbars is also monitored using contact resistivity (ρ_c) utilizing the TLM method. After 1000 hours of exposure to DH, no degradation of the Cu busbars is seen relative to the Ag busbars.

Current-voltage (I-V) measurements using a flash tester (Berger PSS 10 II) are performed. The Cu busbars show increased V_OCand J_SCcompared to the comparative Ag busbars in front busbar examples. Specifically, cells including Cu busbars show a distinct improvement in V_OCand J_SC, relative to cells including Ag busbars. The increase generally corresponds to a 0.6% and 2.59% relative increase in V_OCand J_SC, respectively. It is believed that this increase is attributed to the reduction of metal/silicon contact area, as described above.

A batch of screen printed Al BSF wafers is prepared with rear contact pads. The wafers include front Ag and front Cu prints all with rear Ag busbars. The Cu busbars are printed with the Cu paste as described above. The cells are tabbed manually and tested prior to encapsulation. The cells can be tabbed using typical industry tabbing. In these examples, tabbing can be performed by hand using a soldering iron at 390° C. and flux. Front grid resistance is measured, along with I-V, and Suns Voc to determine quality of the cells and the metallization. The measurement results are shown in FIGS. 25 through 27. The batch shows an improved V_OCand J_SC, again attributed to a decrease in metal/silicon contact area.

Another series of 5 inch (12.7 cm) monocrystalline silicon cells (wafers) are prepared for application of additional Ag and Cu pastes. Example 0 in Table 1 above is repeated for testing of additional Cu electrodes. The cells all include standard Ag front grids (fingers and busbars), and a rear layer of Al (first electrode). Cu electrodes (second electrodes) are printed directly on top of the Al first electrode. Comparative examples with openings in the rear layer of Al (first electrode) with Ag/AI busbars printed on the openings to form second electrodes are indicated in the Figures by “Ag”. Example 0 is indicated by “Cu R” or simply “Cu” in the Figures. All cells are from the same batch (i.e., identically processed up to rear side metallization using either the Ag or the Cu). The cells are tabbed through manual soldering.

Current-voltage (I-V) measurements using a flash tester (PSS 10 II) are performed. Referring to FIG. 28, I-V data for rear Cu busbar Example 0 compared to Ag busbar examples, as second electrodes, is illustrated. The examples both have front Ag busbars, and are configured as i-PERC cells. Referring to FIG. 29, I-V results for Al BSF cells with Cu busbar Example 0 printed on the rear or Ag controls are illustrated. Cells are encapsulated into mini-modules using either EVA or silicone polymers (denoted as Si). Efficiency is comparable and V_OCshows an improvement. FIG. 30 illustrates I-V characteristics of a comparative cell having Ag contacts on Al and an invention cell having Cu contacts, per Example 0, on Al. As shown in FIG. 33, the Cu contact pads do not have a negative impact on cell performance.

Referring to FIG. 31, a cross-sectional SEM micrograph of Example 0 is depicted. Dark grey generally indicates Cu, medium grey generally indicates Sn, white regions generally indicates Bi rich Sn areas, and black areas generally indicate voids and/or epoxy/acrylic binder.

Referring to FIG. 32, a box graph illustrating efficiency percentage of the comparative and invention PV cells is depicted, whereas FIG. 33 illustrates J_SC, and FIG. 34 illustrates V_OCof the examples. Specifically, IV data for samples is measured. Ag examples are 149-1 through 15, and Cu F examples are 149-A through S. Mean values are shown. The comparative and invention examples are the same as described above in the previous example Figures. From the data, it is clearly shown that the use of the Cu busbar of the present invention has a distinct improvement in cell performance. This improvement is believed to come from the reduced recombination by reducing the metal/silicon interface area with reduced high temperature fired Ag metallization points.

FIG. 35 is a cross-sectional optical microscopy photograph illustrating a tabbed busbar of the invention. Specifically, a Cu busbar is printed on top of a SiNx passivation layer and on top a Ag finger and later tabbed. Various components of the invention composition are shown in the cross-section. A direct solder bond to the tabbing/busbar and busbar/finger is shown, as well as the adhesive contact between the Cu busbar and the substrate.

FIG. 36 is a line graph illustrating J_SCof comparative and invention PV cell examples after damp heat aging. FIG. 37 is a line graph illustrating V_OCof the comparative and invention PV cells after damp heat aging, and FIG. 38 is a line graph illustrating sheet resistivity (rs) of the comparative and invention PV cell examples after damp heat aging. From these graphs it is clear that the Cu paste is not degrading performance under corrosive conditions.

One or more of the values described above may vary by ±5%, ±10%, ±15%, ±20%, ±25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated. The disclosure is illustrative including words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be practiced otherwise than as specifically described herein.

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