TW201013700A - Methods using compositions containing submicron particles used in conductors for photovoltaic cells - Google Patents

Abstract

Embodiments of the invention relate to a silicon semiconductor device, and a conductive thick film composition for use in a solar cell device.

Description

201013700 VI. Description of the Invention: TECHNICAL FIELD Embodiments of the present invention relate to a germanium semiconductor device and a conductor thick film composition for use in a solar cell device. [Prior Art] A conventional solar cell structure having a P-type substrate may have a negative electrode on the front side (also referred to as a sun surface or an irradiation surface) of the battery and may have a positive electrode on the back side. Radiation of a suitable wavelength incident on the p-n junction of the semiconductor body is used as an external energy source to create a hole-electron pair in the body. Since there is a potential difference at the p_n junction, the holes and electrons move across the junction in opposite directions and thereby generate a current that can transfer power to the external circuit. Most solar cells are in the form of an already metallized tantalum wafer, which is provided with conductive metal contacts. There is a need in the art for compositions, structures (e.g., semiconductors, solar cells, or photodiode structures) having improved electrical properties, and semiconductor devices (e.g., semiconductors, solar cells, or photodiode devices) and methods of making the same. SUMMARY OF THE INVENTION One embodiment of the present invention relates to a composition comprising: (a) one or more electrically conductive materials; (b) one or more inorganic binders; and (4) an organic medium wherein 1 to 15% of the inorganic components are Submicron particles. In one embodiment, 85-99% of the inorganic component may have (iv) of 1 wom. In one embodiment, the " or multiple conductive materials" may comprise silver. In one embodiment, the - portion of the silver contains submicron particles. In one embodiment, the submicron 140746.doc 201013700 particles have a d50 of 0·1-1 microns. In one embodiment, the submicron particles have a d5 〇 of from 1 to 0.6 microns. In one embodiment, the particles have a bimodal size distribution. The composition may comprise one or more additives selected from the group consisting of: (4) a metal, wherein the metal is selected from the group consisting of Zn, pb, Bi, Gd, Ce, Zr, Ti, Tn'Sn, RU, Co, Fe, ~ and Cr; (b) _ or a plurality of metal oxides selected from the group consisting of Zn, Pb, Bi, Gd, Ce, Zr, Ti, Mn, Sn, RU, Co, Fe, Cu, and Cr; Any compound which produces a metal oxide of (b) after firing; and (d) a mixture thereof. In one embodiment, the additive may comprise Zn ruthenium or a compound that forms Zn ruthenium after firing. In one embodiment, the Zn〇 and/or inorganic binder may comprise sub-micron particles. ZnO can comprise 2% by weight of the total composition. The glass frit may comprise from 1 to 6 parts by weight of the total composition. /. . The electrically conductive material may comprise Ag to Ag which may comprise from 90 to 99% by weight of the solids in the composition. In one embodiment, the inorganic component can comprise from 70 to 95 weight percent per gram of total composition. Another embodiment is directed to a method of fabricating a semiconductor device comprising the steps of: (4) providing a semiconductor substrate, one or more insulating films, and a thick film composition as described herein; (b) applying an insulating film to the semiconductor substrate; (c) applying the thick film composition to the insulating film on the semiconductor substrate, and (d) firing the semiconductor, the insulating film, and the thick film composition, the insulating film may include - or a plurality of selected from the following Components: titanium oxide, tantalum nitride, yttrium: lanthanum, cerium oxide, and cerium oxide/titanium oxide. Yet another embodiment relates to a semiconductor device fabricated by the methods described herein. A pattern relates to a semiconductor device comprising an electrode, wherein the electrode comprises a composition as described herein prior to firing. One embodiment relates to a solar cell comprising a semiconductor device. One embodiment relates to a semiconductor device including a semiconductor substrate, an insulating film, and a front electrode, wherein the front electrode includes one or more components selected from the group consisting of zinc silicate, willemite, and bismuth ruthenate. . [Embodiment]

There is an improved solar cell in the industry that has increased efficiency. Industry Needs A conductor composition suitable for forming a highly increased narrow wire. One aspect of the invention pertains to compositions containing submicron particles. These compositions can be thick film compositions. These compositions can be used to form solar cell electrodes. The electrodes can be located on the front side of the solar cell. In one embodiment, the electrode lines can be relatively thin and have an increased height. As used herein, "thick film composition" means a composition having a thickness of 100 microns after firing the substrate. The thick film composition can contain a conductive material, a glass address, and an organic medium. Thick film compositions can contain other components. The other components used herein are referred to as "additives." The compositions described herein comprise - or a plurality of electrically functional materials and - or a plurality of divided frits. These compositions can be thick film compositions. The material may also contain - or a plurality of additives. Exemplary additives may comprise 3 metals, metal oxides or any compound that is fired. Metal oxides such as sassafras. In one embodiment, the electrical functional powder of Ray, s}xb may be a conductive powder. In a meeting 1, the compositions (e.g., conductor & human n φ ect.) can be used in semiconducting enthalpy. In this embodiment, the dry conductor is placed in a sample, and the semiconductor device can be a solar cell or a photodiode. In still another aspect of this embodiment, the semiconductor device can be one of a wide range of semiconductor devices. In one embodiment, the semiconductor device can be a solar cell. In one embodiment, the thick film compositions described herein can be used in solar cells. In one aspect of this embodiment, the solar cell efficiency can be more than 7% of the reference solar cell. In another embodiment, the solar cell efficiency can be more than 80% of the reference solar cell. Solar cell efficiency can be more than 90% of the reference solar cell. In one embodiment, the ratio of the organic medium to the non-component in the dispersion in the thick film composition can be determined by the method of applying the paste and the type of organic medium used, as determined by those skilled in the art. In one embodiment, the dispersion may contain 7 〇 95% by weight of the inorganic component and (4) % by weight of the organic vehicle (vehicle) to obtain good wettability. In one embodiment, a portion of the inorganic component can be sub-micron particles. In one aspect of this embodiment, the submicron particles can have a d50 of micro. In another aspect, the sub-micron particles may have a d50 of microns. In another aspect, the sub-height wood particles may have a d50 of from -2 to 0.6 microns. % % % In one embodiment, the submicron particles may comprise from 1 to 15 parts by weight of the composition. In other embodiments, the submicron particles may comprise the weight of the composition. In another embodiment, the submicron particles may comprise a combination. The 3-6 weight of the material is in one embodiment. In one aspect, the submicron particles can be incorporated into a portion of the electrically conductive material. 1 to 15% by weight of the electrically conductive material can be submicron J40746.doc 201013700. In another aspect, the 2% by weight of the electrically conductive material can be a submicron particle. In another aspect, 3 - 6 wt% of the conductor composition can be sub-micron particles. In one embodiment, a portion of the composition can have a d50 of 15 to 1 micron. In one aspect of this embodiment, 85 to 99% by weight of the inorganic component of the composition may have a d5 of i,5-i〇micron (in the aspect of the embodiment, in the composition) A portion of the composition may have a d5 2 of 2 〇 7 〇 microns. In one aspect of this embodiment, a portion of the composition may have a d50 of 255 Å. In another aspect, the conductive material may comprise silver. In one aspect, 50-100% by weight of the conductive material may be silver. In another aspect, 70-99% by weight, 70-98% by weight or 8〇95% by weight of the conductive material may be silver. In one aspect of the invention, the composition comprises a frit composition. The frit composition for use in the present invention should be readily prepared by those skilled in the art. For example, t can be used to prepare positive solar energy. The glass frit composition in the composition of the battery electrode. The exemplary frit composition comprises the glass (9) glass. The glass frit composition used in the present invention may comprise 20-24% by weight of Si. 〇2, G2_G8 wt% ALA, 4〇·6〇 weight% Pb〇, and 5_8 weight % b2〇3. In one embodiment, the glass frit composition may optionally comprise 3-7 wt% Ti〇2. In one embodiment, the 'glass frit composition may optionally include _ or a plurality of fluorine-containing components, It includes, but is not limited to, fluoride salts, fluorides, metal oxyfluoride compounds, and the like. These fluorine-containing components include, but are not limited to, PbF2, BiF, 140746.doc 201013700 A1F3, NaF, LiF, KF, CsF, ZrF4, TiF4 and/or ZnF2. In one embodiment, the frit composition may comprise 8_丨3 wt% pbF> 2. In yet another aspect of this embodiment, the thick film composition may comprise electricity Functional powders and glass-ceramic materials dispersed in an organic medium. In one embodiment, the thick film conductor compositions can be used in a semiconductor device. In one aspect of this embodiment, the semiconductor device can be a solar cell or Photoelectric Diodes. Conductive Materials In one embodiment, the thick film composition can comprise a functional phase that imparts suitable electrical functional properties to the composition. In one embodiment, the 'electric functional powder can be a conductive powder. In one embodiment Medium, electricity The energy phase can comprise a conductive material (also referred to herein as conductive particles). For example, the conductive particles can comprise a conductive powder, a conductive foil, or a mixture thereof. In one embodiment, the conductive particles can comprise Ag. In another embodiment The 'conductive particles may include silver (Ag) and Ming (10). In still another embodiment, the conductive particles may comprise, for example, - or a plurality of the following: Cu, Au, Ag, A1 Ag_Pd, Pt_A4. The conductive particles are of the following materials: (1) yttrium, yttrium, U, Au, Agmk alloys; and (7) a mixture of conductive silver particles coated in one embodiment. In embodiments wherein the silver phase L is coated or not coated, the particles are coated, the surfactant is at least partially coated. In the case of power-up, the active agent may comprise -t. In the example of Table 1, the following non-limiting surfactants are: Hard, 14-0746.doc 201013700 Acid, palmitic acid, stearate, palmitate, laurel Acid, palmitic acid, oleic acid, stearic acid, citric acid, myristic acid and linoleic acid, and mixtures thereof. The counter ion can be, but is not limited to, hydrogen, ammonium, sodium, potassium, and mixtures thereof. In one embodiment, the silver may comprise from 60 to 90% by weight of the paste composition. In another embodiment, the silver may comprise 7 〇 85% by weight of the paste composition. In yet another embodiment, the silver can comprise from 75 to 85% by weight of the paste composition. In still another embodiment, the silver may comprise 7 8 _ 8 2 weight 〇 / 〇 of the paste composition.

In one embodiment, the silver may comprise from 90% to 99% by weight of the solids (i.e., other than the organic medium) in the composition. In another embodiment, the silver can comprise from 92 to 97 weight percent lanthanum per gram of solids in the composition. (d) In one embodiment, ♦ may comprise from 93 to 95% by weight of the solids in the composition. As used herein, "particle size" is intended to mean "average particle size"; "average particle size" means a 50% volume distribution size. The volume distribution size can be determined by a variety of methods known to those skilled in the art, including, but not limited to, the LASER diffraction and dispersion methods using a MiCr®trac particle size analyzer. In one embodiment, the granules. In a portion of the conductive material of one of the embodiments, the submicron particles may have a d50 of 〇M micrometers. In another aspect, d50. In another aspect, d50. The 'sub-micron particles may have (1) 微米^^ micron sub-micron particles may have 〇.2_〇 6 microns in one embodiment. In another aspect, the granules. In another aspect, the granules. '1 to 15% by weight of the conductive material can be sub-micron' 2-10% by weight of the conductive material can be 3-6% by weight of the sub-micron conductor composition can be sub-micron 140746.doc -9- 201013700 The - portion of the electrically conductive material may have a thickness of from 1.5 to 10 microns in one aspect of the embodiment, from 85 to 99 weight of the electrically conductive material. /〇 can have a d5〇 of 1.5-10 糌 夕 械. In one aspect of this embodiment, one of the electrically conductive materials has a d50 of 2.0-7.0 microns. In one aspect of this embodiment, a portion of the thunder conductive material 枓 can have a d50 ° additive of 2.5-5 · 0 microns. In one embodiment, the thick film composition can include - or a plurality of additives. In one embodiment, the additive may be selected from one or more of the following: (4) a metal, wherein the metal is selected from the group consisting of Zn, pb, m, (5), zr, and dibutyl

Mn ' Sn ' Ru ' Co ' Fe ' Γι, a 〇

Cu and Cr; (b) One or more metal oxides selected from the group consisting of Zn, pb, m, and . , Zr, 耵,

Mn, Sn, Ru, Co, Fe, r""p C and Cr, (c) any compound which produces a metal oxide of (b) after firing; and (d) a mixture thereof. In one embodiment The additive may comprise a cerium additive. The & additive may comprise one or more of the following: (a) Zn, (the kiss gold oxide, (4) any compound that produces a metal oxide of Zn after firing, and (4) In one embodiment, the Zn-containing additive may comprise Zn resin. The Zn-containing additive may comprise Zn 在. In one embodiment, the ～ part of ZnQ may comprise sub-micron particles. In one embodiment, Zn〇 may be present in the composition in a range of from 2% to 1% by weight of the total composition. In one embodiment, cerium may be present in the range of "% by weight of the total composition." Wherein, Zn〇 may be present in the range of 4-6 wt% of the total complex. 140746.doc -10. 201013700 Organic Medium In one embodiment, the thick film composition described herein may comprise an organic medium by ( For example, mechanical mixing allows the inorganic component to be mixed with an organic medium to form a paste. A variety of inert viscous materials are used as the organic medium. In the case of "real", the 'organic medium can be a medium in which the inorganic component can be sufficiently stabilized. In one embodiment, the rheology of the medium allows the basin to be Certain application characteristics are imparted to the composition comprising: a stable solid: • dispersed, suitable screen printing and thixotropy, suitable wettability of the substrate and paste solids, good drying rate and good firing characteristics The organic medium used in the 'thick film composition' may be a non-aqueous inert liquid in one embodiment. The invention encompasses the use of a variety of organic vehicles which may or may not contain thickeners, stabilizers and/or other common additives. A solution in which the polymer is dissolved in a solvent. In one embodiment, the organic vehicle may also comprise one or more components such as a surfactant. In one embodiment, the polymer may be ethyl cellulose. The polymer comprises ethyl ethyl cellulose, wood rosin, a mixture of ethyl cellulose and a phenolic resin, a polymethacrylate of a lower alcohol number, and a monobutyl ether of a diol monoacetate, or a mixture thereof. In one embodiment, the solvent used in the thick film composition described herein comprises an ester alcohol and a tank (eg, heart or diterpene alcohol) or a mixture of other solvents such as kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol acetate, hexanediol, and high boiling alcohols and alcohol esters. In another embodiment The organic medium may comprise a volatile liquid that promotes rapid hardening after application to the substrate. In one embodiment, for example, the polymer may comprise up to 8 weight of the total composition 140746.doc 201013700 Available organic media will range from % to 11% by weight The thick film silver composition is present in the organic medium to a predetermined screen printable viscosity. The fired thick film composition can be removed during the drying and firing of the semiconductor device. In one aspect, the frit and the additive may be sintered to form an electrode during firing. The fired electrode can comprise components, compositions, and the like that result from the firing and sintering process. In one aspect of this embodiment, the semiconductor device can be a solar cell or a photodiode. Method of Manufacturing a Semiconductor Device One embodiment relates to a method of fabricating a semiconductor device. In one embodiment, a semiconductor device can be used in a solar cell device. The semiconductor device can comprise a front side electrode' wherein the 'before firing' front side (irradiation side) electrode can comprise a composition as described herein. In one embodiment, a method of fabricating a semiconductor device includes the steps of: (a) providing a semiconductor substrate; (b) applying an insulating film to the semiconductor substrate; (c) applying the composition described herein to the insulating film; The device is fired. Exemplary semiconductor substrates used in the methods and apparatus described herein are to be understood by those skilled in the art and include, but are not limited to, single crystal, polycrystalline germanium, germanium, and the like. The semiconductor substrate can have a junction. The semiconductor substrate may be doped with a collar and a collar to form a p/n junction. The method of doping the semiconductor substrate should be understood by those skilled in the art. The dimensions (length X width) and thickness of the semiconductor substrate can vary, as will be appreciated by those skilled in the art. In a non-limiting example, the thickness of the semiconductor substrate can be 50-500 microns, 100-300 microns, or 14"-200 microns. In a non-limiting example, the length and width of the semiconductor substrate can be equal to 1 〇〇 25 〇 mm, 125-200 mm, or 125-156 mm. Exemplary insulating films used in the methods and devices described herein are known to those skilled in the art and include, but are not limited to, tantalum nitride, hafnium oxide, titanium oxide, SiNx:H, hydrogenation Crystalline tantalum nitride, and tantalum oxide/titanium oxide film. The insulating film can be formed by PECVD, CVD, and/or other techniques known to those skilled in the art. In the embodiment in which the insulating film is tantalum nitride, the tantalum nitride film can be formed by plasma-thin chemical vapor deposition (PECVD), thermal CVD process, or physical vapor deposition (pVD). In the embodiment in which the insulating film is an oxidized oxide, the oxidized oxide film may be formed by thermal oxidation, thermal CVD, plasma CVD, or PVD. The insulating film (or layer) may also be referred to as an anti-reflective coating (ARC). The compositions described herein can be applied to an ARC coated semiconductor substrate by a variety of methods known to those skilled in the art, including, but not limited to, screen printing, ink jet, coextrusion. , injection coating, direct writing, and aerosol inkjet. In one embodiment, the composition can be applied to a substrate using the methods and apparatus set forth in U.S. Patent Application Publication No. 2003/0100824, the disclosure of which is incorporated herein by reference. The composition can be applied in the form of a pattern. The composition can be applied in a predetermined shape and at a predetermined position. In one embodiment, the composition can be used to form both the conductive fingers of the front side electrode and the bus bar. In one embodiment, the width of the conductive finger lines can be 10-200 microns, 40-150 microns, or 6 〇 1 〇〇 microns. In one embodiment, 140746.doc -13- 201013700 the width of the conductive finger line can be 丨〇 i 〇〇 micrometers, 15 _ 80 micrometers, or 20-75 micrometers. In one embodiment, the conductive finger lines may be 5-50 microns, 1" to 35 microns, or 15-30 microns thick. In another embodiment, the composition can be used to form a conductive 8 inch contact finger structure. As will be appreciated by those skilled in the art, the composition coated on the Arc coated semiconductor substrate can be dried, for example, for 5 to 1 minute, and subsequently fired. In one embodiment, volatile solvents and organic materials can be removed during the drying process. The firing conditions should be known to those skilled in the art. Under exemplary non-limiting firing conditions, the tantalum wafer substrate is heated to a maximum temperature between 600 and 900 °C for i seconds to 2 minutes. In one embodiment, the highest wafer temperature achievable during firing is between 65 〇 and 800 C for 1 〇 sec. In another embodiment, the electrode formed of the conductor thick film composition may be fired in an atmosphere composed of a mixed gas of oxygen and nitrogen. This firing process removes and sinters the organic medium from the frit and Ag powder in the conductor thick film composition. In another embodiment, the electrode formed from the thick film composition of the conductor can be fired in an inert atmosphere free of oxygen at a temperature above the removal temperature of the organic medium. The firing process sinters or melts a base metal conductive material, such as copper, in the thick film composition. In one embodiment, during firing, the fired electrode (preferably finger, ' configuration) can react with and penetrate the insulating film to form electrical contact with the germanium substrate. In other embodiments, other conductive and device reinforcing materials are applied to the opposite regions of the semiconductor device prior to firing and cofired or subsequently fired with the compositions described herein. The opposite type of device is located on the opposite side of the device's phase 140746.doc 201013700. Materials such as βH are used as electrical contacts, purification layers, and solderable fixtures. In one embodiment, the opposing region may be located on the non-irradiated (back) side of the device. In one aspect of this embodiment, the back side conductive material may contain aluminum. Illustrative backside aluminum-containing compositions and methods of application are described, for example, in U.S. Patent No. 2006/0272700, which is incorporated herein by reference. In another aspect, the solderable fixing material may contain aluminum and silver. An exemplary fixed composition comprising aluminum and silver is described, for example, in U.S. Patent No. 2006/0231803, which is incorporated herein by reference. In another embodiment, the material applied to the opposite region of the device is adjacent to the materials described herein by the ρ and η regions formed side by side. These devices place all metal contact materials on the non-irradiated (back) side of the device to maximize incident light on the (positive) side of the illumination. The semiconductor device can be fabricated from a structural element composed of a semiconductor substrate having a junction and a tantalum nitride insulating film formed on a main surface thereof. A method of manufacturing a semiconductor device includes the steps of applying (e.g., coating and printing) a conductive thick film composition capable of penetrating an insulating film to a predetermined film in a predetermined shape and at a predetermined position, and then performing firing to make a thick film combination of the conductor The material melts and flows through the insulating film to achieve electrical contact with the As-yed substrate. The conductor thick film composition is a thick film paste composition, as described herein, which consists of a silver powder, a Mn-containing additive, a glass or glass powder mixture (having a 300-60 (TC softening point, dispersed in an organic vehicle) And other metal/metal oxide additives as the case may be. One embodiment of the invention pertains to a semi-conductor 140746.doc 15 201013700 body device made by the method described herein. The device containing the composition described herein may contain tannic acid Zinc is as described above. One embodiment of the invention pertains to a semiconductor device fabricated by the above method. Other substrates, devices, methods of manufacture, and the like that can be used with the thick film compositions described herein are set forth in U.S. Patent Application The disclosures of the entire contents of each of the entireties are hereby incorporated by reference in the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of The polymer is dissolved in an organic solvent to prepare an organic medium. Other ingredients including silver powder, glass frit, oxidized and other additives are added to the organic medium. The resulting mixture was dispersed by a 3-roll-grinding process as is known in the art of thick film paste manufacturing to form compositions I, π and ΙΠ shown in Table 1. Prior to printing, via a Roki 40L-SHP-200XS filter capsule pair The paste from Compositions I and II was subjected to filtration. The composition was used without filtration. Reusable by ID/OD 50/75 μm at room temperature by a 3D-450 Smart PumpTM printer manufactured by nScrypt The ceramic tip evaluates the paste. The pumping pressure is between 1 psi and 1 psi. The printing speed is between 200 mm/sec and 300 mm/sec. The gap between the nib and the substrate surface is 150 μm. Several sets of 1 inch long 4 inch long lines were printed, allowed to dry in a 150 ° C box furnace for 20 minutes, and fired in a belt furnace at a peak temperature of 850 ° C for 2 minutes. 140746.doc •16 - 201013700

Table ι·Detailed composition of silver paste composition----- Composition I Silver powder I 81.05 ----- Silver powder II Silver powder III ----_____ ------ Glass frit I Glass frit II Glass frit III oxidation word - 5.5 organic medium 10.95

Composition II 81.05 5^ 10.95

Composition III 81.05 2.5 5.5 10.95

* Take the weight of the total composition. / 银 Silver powder I, a mixture of spheres and flakes D50 = 4.60, D95 = l〇.73 microns. Silver powder π, spherical powder 'and size is 1 〇, age 171, D95 = 4.41 μm and surface area 〇 44 m gram. Silver powder is in spherical powder and has a size of D95M.67 microns and a solids of 99 5%. Its surface area is 1 mil 2 / gram. Glass frit I 'SiO 2 23.0%, a12 〇 3 0.4%, Pb 〇 58.8% and B2 〇 3 7.8%, based on the weight % of the glass composition, and the dimensions are D1 〇 = 〇 36, D50 = 0.61 and D95 = 1.44 Micron. And the size is D10=0.88 glass frit II, SiO2 22.08%, Al2〇3 0.38%, PbO 46_68%, B2〇3 6.79%, Ti02 5.86% and PbF2 10.72%, based on the weight % of the glass composition, and the size is D10 = 0.42, D50 = 0.77 and D90 = 1.96 microns. 140746.doc -17- 201013700 Glass frit III, Si〇2 22.08%, Al2〇3 0.38%, PbO 46,68%, B203 6.79%, Ti02 5.86% and PbF2 10.72%, based on the weight % of the glass composition, And the dimensions are Dl0 = 0 34, D5 〇 = 〇 5 〇 and D95 = 〇 89 microns. Zinc oxide was purchased from Aldrich Chemicals. Example I. The composition was able to pass at a pumping pressure below 50 psi, the micron nib and the nib blocked in less than 5 minutes. The resulting best firing system is 8 microns wide and 13 microns high. Example II. At a pumping pressure below 60 psi, the composition can pass through a 75/ΐ25® micron tip and the pen is blocked in less than 30 minutes. The resulting optimum firing line is 100 microns wide and 12 microns high. Example III. Composition II can pass through a 50/75 micron tip and pass through a period of at least 3 minutes at a pumping pressure between 1 psi and 1 psi; brush. The resulting optimum firing line was 89 microns wide and 19 microns high. Example IV. Compositions with a weight percentage of 95.5 and 4.5 at a pumping pressure of between 10 Torr and (10) psi and a composition of composition (1) can pass through a 50/75 micron tip and stop for at least 3 hours. Printing. The fired wire is 67 microns wide and 25 microns high. Example V. At a pumping pressure greater than 30 psi, the composition m cannot be printed through a 50/75 micron pen tip. Blockage occurs at $2 nibs. For example Vi·纟 at a pumping pressure greater than 60 psi, composition m can be printed through a 75/125 micron tip. Under (iv), printing continues for less than... The tip of the pen is blocked. Doc •18· 201013700 Example VI1·Prepare a series of composition Π& ΠΙ blends with a weight ratio between 90 and ι to 10 and 9 并 and perform printing. Once the composition exceeds 30% '50/ The 75 micron nib was blocked in 1 minute. Example VIII. Analysis of the efficiency of the above printed substrate. An exemplary efficiency test is provided below. It is expected that the solar cell from Example IV is more efficient than the solar cell from other examples. effectiveness Test Procedure - Efficiency Tests the conversion efficiency of solar cells constructed according to the methods described herein. An exemplary method of testing efficiency is provided below. In one embodiment, a solar cell constructed in accordance with the methods described herein is placed in a commercial IV test. The instrument is used to measure efficiency (ST_1000). The Xe arc lamp in the tester simulates sunlight with known intensity and radiates the front surface of the battery. The tester uses multi-point contact method to measure current at about 400 load resistance settings. (I) and voltage (V) to determine the curve of the battery. Calculate both the fill factor (FF) and the efficiency (Eff) according to the curve. [Schematic Description of the Drawings] Figs. 1A to 1F show a process flow chart for explaining the fabrication of a semiconductor device. The reference numerals shown in Figs. 1A to 1F are explained as follows. 10: P-type germanium substrate 20: n-type diffusion layer 30: tantalum nitride film, titanium oxide film or hafnium oxide film 4: P+ layer (back surface electric field) , BSF) 60: Aluminum paste formed on the back surface 140746.doc •19· 201013700 61 : The back electrode (obtained by firing the back aluminum paste) 70: Silver or silver/aluminum paste 71 formed on the back side : back Silver or silver/aluminum electrode (obtained by firing a back silver paste) 5: Silver paste 501 formed on the front side according to the present invention: front side silver electrode of the present invention (by firing a front silver paste [ Explanation of main component symbols] 10 p-type 矽 substrate 20 n-type diffusion layer 30 nitriding film / titanium oxide film / oxidized stone film 40 Ρ + layer 60 aluminum paste formed on the back surface 61 back electrode 70 on the back Silver or silver/aluminum paste 71 formed on the back Silver or silver/Ming electrode 500 Silver paste 501 formed on the front side according to the present invention is formed by the front silver electrode of the present invention)

140746.doc -20-

Claims (1)

201013700 VII. Patent Application Range: A method of manufacturing a semiconductor device, comprising the steps of: (a) providing a semiconductor substrate, one or more insulating films, and a thick film composition; (b) applying the insulating film to the semiconductor substrate (c) applying the thick film composition to the insulating film on the semiconductor substrate, and 2. (d) firing the semiconductor, insulating film and thick film composition, wherein the thick film composition comprises: (a) - or a plurality of conductive materials; (b) - or a plurality of inorganic binders; and (c) organic Medium, wherein 1 to 15% of the inorganic components are submicron particles. The method of claim 1, wherein the insulating film comprises one or more selected from the group consisting of ruthenium, oxidized, nitrided, oxidized, and cerium oxide/titanium oxide. 3. 5.6. The method of claim 1 is 10 micron d5〇. The method of claim 1 is as claimed in claim 4, wherein the method of claim 1 is d50 〇 wherein 85-99% of the inorganic components have 1.5- wherein the one or more electrically conductive materials comprise silver. Wherein the sub-micron particles comprise silver. Wherein the sub-micron particles have a size of from 0.1 to 1 micron 7, as claimed in claim 1 of the formula d5. 8. The method of claim 1 wherein the sub-micron particles have a thickness of from 0.1 to 0.6. wherein the inorganic components have a bimodal size of 140746.doc 201013700. 9. The method of claim 1, wherein the thick film composition further comprises one or more additives. 10. The method of claim 9 wherein the one or more additives comprise a component selected from the group consisting of: (4) a metal, wherein the metal is selected from the group consisting of Zn, Pb, Bi, Gd, Ce, Zr, Ti. , Mn, %, Ru, c〇, Fe, cu and Cr; (b) - or a plurality of metal oxides selected from the group consisting of zn, Pb, Gd, Ce, Zr, Ti, Mn, %, Ru , c〇, 、, cu And Cr; (c) any compound which produces (b) the metal oxides after firing; and (d) a mixture thereof. 11. The method of claim 1 (), wherein the one or more inorganic additives comprise ZnO. The method of claim 5, wherein the sub-micron particles further comprise Zn〇 and an inorganic binder. The method of claim 1, wherein the one or more inorganic binders comprise a glass frit. The method of claim 1, wherein the inorganic components comprise from 70 to 95% by weight of the total composition. 140746.doc -2 -