TW201332897A - Barrier layer forming composition, method for producing photovoltaic cell substrate, and method for producing photovoltaic cell element - Google Patents

Abstract

The present invention provides a barrier layer forming composition including a metal compound which contains alkali-earth metal or alkali metal; dispersion medium; and a thixotropic agent.

Description

Barrier layer forming composition, solar cell substrate manufacturing method, and solar cell element manufacturing method

The present invention relates to a barrier layer forming composition, a method for producing a solar cell substrate, and a method for producing a solar cell element.

The manufacturing steps of the conventional tantalum solar cell element will be described. First, in order to promote the light confinement effect to achieve high efficiency, a p-type germanium substrate having a textured structure formed on the surface to be the light receiving surface is prepared, and then, phosphorous oxychloride (POCl) is prepared. ₃ ) A mixed gas atmosphere of nitrogen and oxygen is subjected to treatment at 800 ° C to 900 ° C for several tens of minutes to form an n-type diffusion layer. Then, an electrode paste containing silver (Ag) or the like is applied to the light-receiving surface, and an electrode paste containing aluminum or the like is applied to the back surface side to be baked, thereby obtaining a solar cell element.

However, since sunlight does not enter directly below the electrode on the light-receiving surface side, this portion does not generate electricity. Therefore, a back electrode type solar cell has been developed which has no electrode on the light receiving surface and has an n-type diffusion layer and a p ⁺ type diffusion layer on the back surface (for example, refer to Japanese Laid-Open Patent Publication No. 2011-507246) .

A method of forming the above-described back electrode type solar cell will be described. A barrier layer is formed on the entire surface of the light receiving surface and the back surface of the n-type germanium substrate. Here, the barrier layer has a function of controlling diffusion of impurities in the germanium substrate. Next, a part of the barrier layer on the back surface of the ruthenium substrate is removed to form an opening. Then, when the p-type impurity is diffused from the opening of the barrier layer to the back surface of the germanium substrate, the p ⁺ -type diffusion layer is formed only in the region corresponding to the opening. Next, after all the barrier layers on the back surface of the ruthenium substrate were removed, a barrier layer was formed on the entire surface of the back surface of the ruthenium substrate again. Then, a part of the barrier layer in a region different from the region in which the p ⁺ -type diffusion layer is formed is removed to form an opening, and the n-type impurity is diffused from the opening to the back surface of the germanium substrate to form an n ⁺ -type diffusion layer. Then, the barrier layer on the back surface of the ruthenium substrate is entirely removed, whereby a region in which the p ⁺ -type diffusion layer is formed and a region in which the n ⁺ -type diffusion layer is formed are formed on the back surface. Further, the back electrode type solar cell is completed by forming a texture structure, an antireflection film, a passivation film, an electrode, or the like.

As the barrier layer, there has been proposed a method of forming an oxide film formed on the surface of a substrate by a thermal oxidation method (for example, see JP-A-2002-329880). On the other hand, a method of forming a barrier layer using a masking paste containing a cerium oxide (SiO ₂ ) precursor has also been proposed (for example, refer to Japanese Laid-Open Patent Publication No. 2007-49079).

However, in the method of forming an oxide film on the surface of the substrate by the thermal oxidation method described in Japanese Laid-Open Patent Publication No. 2002-329880, since the process is long, the manufacturing cost is increased. In the method of using a masking paste containing a SiO ₂ precursor described in Japanese Laid-Open Patent Publication No. 2007-49079, the method is to physically prevent a donor element or an acceptor element (hereinafter collectively referred to as "doping". In the method of diffusing the agent, and the barrier layer containing SiO ₂ is difficult to form a dense film, pinholes are easily formed, and thus it is difficult to sufficiently prevent diffusion of the dopant to the substrate. Further, in the conventional masking paste, if it is applied to a substrate or placed in a drying step, it is difficult to maintain the shape of the application layer, and the desired pattern shape is not maintained.

The present invention has been made in view of the above conventional problems, and it is an object of the invention to provide a barrier layer-forming composition capable of sufficiently preventing diffusion of a donor element or an acceptor element onto a semiconductor substrate and suppressing a shape change after pattern formation. A method for producing a substrate for a solar cell and a method for producing a solar cell element.

Specific methods for solving the above problems are as follows, and the present invention includes the following embodiments.

<1> A composition for forming a barrier layer, comprising: a metal compound containing an alkaline earth metal or an alkali metal, a dispersion medium, and a thixotropic agent.

The composition for forming a barrier layer according to the above <1>, wherein the thixotropic agent comprises a polyether compound, a fatty acid decylamine, an organic filler, an inorganic filler, hydrogenated castor oil, urea urethane. One of a group consisting of a guanamine, a polyvinylpyrrolidone, an anthrone-based viscosifying gelling agent, and an oil-based gelling agent on.

The composition for forming a barrier layer according to the above <1>, wherein the thixotropic agent contains one or more selected from the group consisting of a polyether compound, a fatty acid guanamine, and an inorganic filler. .

The composition for forming a barrier layer according to any one of the above aspects, wherein the thixotropic agent contains at least a polyether compound, and the polyether compound comprises the following formula (1) Compounds indicated:

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, n represents an integer of 1 or more, and R ² represents an exoethyl group or a propyl group).

The composition for forming a barrier layer according to any one of the above aspects, wherein the thixotropic agent contains at least a polyether compound, and the number average molecular weight of the polyether compound is 300 to 5,000,000. .

The composition for forming a barrier layer according to any one of the above aspects, wherein the thixotropic agent contains at least a polyether compound, and the polyether compound has a number average molecular weight of 10,000 to 50,000. .

<7> The barrier layer formation according to any one of the above items <1> to <6> The composition wherein the thixotropic agent contains at least a polyether compound, and the polyether compound comprises at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and poly(ethylene glycol-propylene glycol) copolymer. .

The composition for forming a barrier layer according to any one of the above aspects, wherein the thixotropic agent contains at least a fatty acid decylamine, and the fatty acid decylamine comprises the following general formula (2) a compound represented by the formula (3), the formula (4) or the formula (5): R ⁴ CONH ₂ (2)

R ⁴ CONH-R ⁵ -NHCOR ⁴ ......(3)

R ⁴ NHCO-R ⁵ -CONHR ⁴ ......(4)

R ⁴ CONH-R ⁵ -NR ⁶ R ⁶ ......(5)

(In the general formula (2), the general formula (3), the general formula (4), and the general formula (5), R ⁴ and R ⁶ each independently represent an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and R ⁵ represents Alkene having a carbon number of 1 to 10).

The composition for forming a barrier layer according to any one of the above aspects, wherein the thixotropic agent contains at least a fatty acid decylamine, and the fatty acid decylamine comprises a decylamine selected from the group consisting of decylamine One or more of the group consisting of N,N'-methylenebisstearate and dimethylaminopropyl decylamine stearate.

The composition for forming a barrier layer according to any one of the above aspects, wherein the thixotropic agent contains at least a fatty acid decylamine, and the fatty acid decylamine is evaded or decomposed at 400 ° C or lower.

<11> The barrier layer formation according to any one of the above <1> to <10> A composition wherein the thixotropic agent comprises at least an inorganic filler, and the inorganic filler comprises fumed silica.

<12> The composition for forming an impurity diffusion layer according to the above <11>, wherein the surface of the smoked cerium oxide is hydrophobized.

The composition for forming a barrier layer according to any one of the above aspects, further comprising an organic binder.

The composition for forming a barrier layer according to the above <13>, wherein the organic binder contains one or more selected from the group consisting of an acrylic resin, a cellulose resin, and a butyral resin.

The composition for forming a barrier layer according to any one of the above aspects of the present invention, wherein the alkaline earth metal or alkali metal-containing metal compound among all nonvolatile components of the barrier layer forming composition The total mass ratio is 0.5% by mass or more and less than 95% by mass.

The composition for forming a barrier layer according to any one of the above aspects, wherein the metal compound containing an alkaline earth metal or an alkali metal is selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, and cesium. One or more of the groups consisting of 铯, 铍, 铍, 锶, 钡, and radium are used as the metal element.

The composition for forming a barrier layer according to any one of the above aspects, wherein the metal compound containing an alkaline earth metal or an alkali metal is selected from the group consisting of magnesium oxide, calcium oxide, potassium oxide, and carbonic acid. One or more of the group consisting of magnesium, calcium carbonate, magnesium sulfate, calcium sulfate, calcium nitrate, magnesium hydroxide, and calcium hydroxide.

<18> The barrier layer formation according to any one of the above <1> to <17> In the composition, the dispersion medium contains one or more selected from the group consisting of water, an alcohol solvent, a glycol monoether solvent, an isobornylcyclohexanol, and a terpene solvent.

The composition for forming a barrier layer according to any one of the above-mentioned items, wherein the viscosity at 25 ° C is 0.5 Pa. s~400 Pa. s.

The composition for forming a barrier layer according to any one of the above-mentioned items, wherein the barrier layer is used to partially form a barrier layer on a semiconductor substrate, and the barrier layer is for suppressing a donor element or The diffusion of the acceptor element to the semiconductor substrate.

<21> A semiconductor substrate with a barrier layer, comprising a semiconductor substrate and a barrier layer, the barrier layer being the barrier layer according to any one of the above <1> to <19>, which is applied to the semiconductor substrate. The formation composition is obtained by removing at least a part of the dispersion medium.

(22) A method for producing a substrate for a solar cell, comprising: applying a barrier layer-forming composition according to any one of the above items <1> to <19> to a pattern to form a barrier layer And a step of diffusing a donor element or an acceptor element from a portion of the semiconductor substrate on which the barrier layer is not formed, and partially forming an impurity diffusion layer in the semiconductor substrate.

The method for producing a substrate for a solar cell according to the above aspect, wherein the method of applying the composition for forming a barrier layer is a printing method or an inkjet method.

<24> A method of manufacturing a solar cell element, including using such as <22> The step of forming an electrode on the impurity diffusion layer of the solar cell substrate obtained by the production method described in <23>.

According to the present invention, it is possible to provide a barrier layer-forming composition capable of sufficiently preventing diffusion of a donor element or an acceptor element onto a semiconductor substrate and suppressing a shape change after pattern formation, and a solar cell using the barrier layer-forming composition. A method of manufacturing a substrate and a method of manufacturing a solar cell element.

10‧‧‧n type semiconductor substrate

11‧‧‧Block formation composition

12, 13‧‧‧Developing diffusion materials

12', 13'‧‧‧ Burning materials for coating diffusion materials

14‧‧‧n ⁺ type diffusion layer

15‧‧‧p ⁺ diffusion layer

16‧‧‧Anti-reflective film

17‧‧‧ Passivation film

18, 19‧‧‧ electrodes

FIG. 1 is a cross-sectional view conceptually showing an example of a manufacturing procedure of a solar cell substrate and a solar cell element of the present invention.

First, the composition for forming a barrier layer of the present invention will be described. Next, a method for producing a substrate for a solar cell using a composition for forming a barrier layer and a method for producing a solar cell element will be described. In addition, the term "step" in the present specification includes not only independent steps but also a case where it is impossible to clearly distinguish from other steps, and is included in the term as long as the desired purpose of the step is achieved. In the present specification, "~" means a range including the numerical values described before and after the respective values as the minimum value and the maximum value. Further, in the present specification, a plurality of substances satisfying the respective components are present in the composition, and the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified.

<Composition for forming a barrier layer>

The barrier layer-forming composition of the present invention contains a metal compound (hereinafter also referred to as "specific metal compound") containing an alkaline earth metal or an alkali metal, a dispersion medium, and a thixotropic agent. The barrier layer formed of the barrier layer-forming composition of the present invention inhibits diffusion of a donor element or an acceptor element as a dopant to a semiconductor substrate. Therefore, by forming a barrier layer using the barrier layer-forming composition of the present invention in a region of the semiconductor substrate where the donor element or the acceptor element is to be inhibited from diffusing, the donor element and the acceptor in the above region can be sufficiently hindered. The diffusion of elements. That is, a doped region (impurity diffusion layer) can be selectively formed on the semiconductor substrate. Regarding the reason, it can be considered as follows.

If a barrier layer-forming composition comprising a specific metal compound and a thixotropic agent is applied onto a semiconductor substrate to form a barrier layer, a dopant compound containing a dopant is used to perform diffusion treatment of the dopant, and then the specific metal is used. A reaction occurs between the compound and the dopant compound. Since this reaction is higher in reactivity than the reaction between the dopant compound and the semiconductor substrate, it is considered that the diffusion of the donor element or the acceptor element to the semiconductor substrate is inhibited.

Further, in general, a doping compound containing a donor element or an acceptor element is phosphorus oxide, phosphorus oxychloride, boron oxide or the like, and these compounds are all acidic compounds (or compounds which react with water to exhibit acidity). Therefore, a specific metal compound is particularly preferably a basic compound. Since the acid-base reaction between the specific metal compound of the basic compound and the dopant compound is high, the reactivity of the acid-base reaction is high, and therefore it is considered that the diffusion of the donor element or the acceptor element into the semiconductor substrate can be more effectively suppressed.

In addition, specific metal compounds are at high temperatures (for example, above 500 ° C) Since it is also stable, when the donor element or the acceptor element is thermally diffused to the semiconductor substrate, the effects of the present invention can be sufficiently exerted.

In addition, when the specific metal compound is dissolved in the semiconductor substrate, it does not function as a recombination center of the carrier in the semiconductor substrate. Therefore, it is possible to suppress a problem that the conversion efficiency of the semiconductor substrate is lowered.

(metal compound containing alkaline earth metal or alkali metal)

The barrier layer-forming composition of the present invention contains one or more kinds of metal compounds (specific metal compounds) containing an alkaline earth metal or an alkali metal. By containing a specific metal compound, it is possible to inhibit the diffusion of the donor element or the acceptor element into the semiconductor substrate.

The specific metal compound may be a liquid at normal temperature (about 20 ° C) or a solid. In order to maintain sufficient barrier properties at high temperatures, it is necessary to have chemical stability at a high temperature. From this viewpoint, it is preferably a solid at a high temperature (for example, 500 ° C or higher) at which heat is diffused. Here, examples of the specific metal compound include a metal oxide containing an alkaline earth metal or an alkali metal, and a metal salt containing an alkaline earth metal or an alkali metal.

The specific metal compound is not particularly limited, and is preferably a material which changes to a basic compound at a high temperature of 700 ° C or higher at which the donor element or the acceptor element is thermally diffused. Further, in terms of exhibiting strong alkalinity, the specific metal compound preferably contains 1 selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, rubidium, cesium, lanthanum, cerium, lanthanum, and radium. More preferably, the metal element is one or more selected from the group consisting of magnesium, calcium, barium, potassium, and sodium, and more preferably contains one or more selected from the group consisting of magnesium, calcium, barium, potassium, and sodium. One or more of the group consisting of magnesium, calcium, and potassium is preferably one or more selected from the group consisting of magnesium and calcium, from the viewpoint of low toxicity and ease of availability.

In view of chemical stability, the specific metal compound is preferably one or more selected from the group consisting of metal oxides, metal carbonates, metal nitrates, metal sulfates, and metal hydroxides. More preferably, it is one or more selected from the group consisting of metal oxides, metal carbonates, and metal hydroxides, and the metal oxide, metal carbonate, metal nitrate, metal sulfate, and metal hydroxide are contained. One or more of the groups consisting of the above metal elements are selected. These specific metal compounds may be used alone or in combination of two or more.

The specific metal compound is preferably one or more selected from the group consisting of sodium oxide, potassium oxide, lithium oxide, calcium oxide, magnesium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide. a metal oxide such as oxidized radium oxide and a composite oxide thereof; sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, a metal hydroxide such as barium hydroxide or radium hydroxide; a metal carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, barium carbonate, barium carbonate, barium carbonate, barium carbonate or radium carbonate; Metal nitrates such as sodium nitrate, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, barium nitrate, barium nitrate, barium nitrate, barium nitrate, barium nitrate, radium nitrate, etc.; sodium sulfate, potassium sulfate, lithium sulfate, calcium sulfate, sulfuric acid Metal sulfates such as magnesium, barium sulfate, barium sulfate, barium sulfate, barium sulfate, barium sulfate, and radium sulfate. More preferably, the specific metal compound is selected from the group consisting of the above metal oxides and composite oxidation of these One or more of the group consisting of a substance, a metal hydroxide, and a metal carbonate.

Among these compounds, the specific metal compound is preferably selected from the group consisting of sodium carbonate, sodium oxide, potassium carbonate, potassium oxide, calcium carbonate, calcium hydroxide, calcium oxide, magnesium carbonate, from the viewpoint of low toxicity and ease of availability. One or more selected from the group consisting of magnesium hydroxide, magnesium sulfate, calcium sulfate, calcium nitrate, and magnesium oxide, more preferably selected from the group consisting of magnesium oxide, calcium oxide, potassium oxide, magnesium carbonate, calcium carbonate, magnesium sulfate, and sulfuric acid. One or more selected from the group consisting of calcium, calcium nitrate, magnesium hydroxide, and calcium hydroxide, and more preferably selected from the group consisting of calcium carbonate, calcium oxide, potassium oxide, calcium hydroxide, magnesium carbonate, and magnesium oxide. One or more of the group is particularly preferably calcium carbonate.

When the specific metal compound is solid at normal temperature and exhibits a particle shape, the particle diameter of the particle is preferably 30 μm or less, more preferably 0.01 μm to 30 μm, and particularly preferably 0.02 μm to 10 μm. Particularly preferred is 0.03 μm to 5 μm.

When the particle diameter is 30 μm or less, the application portion on the semiconductor substrate can uniformly and more effectively inhibit the diffusion (doping) of the donor element or the acceptor element.

In addition, when the particle diameter is 0.01 μm or more, the specific metal compound is more easily dispersed in the composition for forming a barrier layer, and the application characteristics are further improved. Further, a specific metal compound may also be dissolved in the dispersion medium.

Here, the particle diameter represents a volume average particle diameter, and can be measured by a laser scattering diffraction particle size distribution measuring apparatus or the like. The relationship between the intensity of the scattered light of the laser light irradiated to the particles and the angle can be detected, and the volume average particle diameter can be calculated based on the Mie scattering theory. There is no special limit to the dispersion medium at the time of measurement. However, it is preferable to use a dispersion medium which does not dissolve the particles to be measured.

The method of obtaining the above-mentioned particles having a particle diameter of 30 μm or less is not particularly limited, and for example, it can be obtained by pulverization treatment. The pulverization method may be a dry pulverization method or a wet pulverization method. The dry pulverization method may employ a jet mill, a vibration mill, a ball mill, or the like. The wet pulverization method may employ a beads mill, a ball mill, or the like.

When the impurities caused by the pulverizing device are mixed in the barrier layer-forming composition during the pulverization treatment, there is a concern that the life of the carrier in the semiconductor substrate is lowered. Therefore, the material of the pulverization container, the beads, the beads, or the like is preferably A material having a small influence on the semiconductor substrate is selected. The material of the container or the like which is suitably used for pulverization is preferably alumina or partially stabilized zirconia. Further, in addition to the pulverization method, a gas phase oxidation method, a hydrolysis method, or the like can be used.

Further, the particles may be a carrier containing a compound other than a specific metal compound (for example, cerium oxide particles), and a material carrying a specific metal compound may be coated or dispersed on the surface of the carrier. In this form, the effective surface area of the specific metal compound can be enlarged, and there is a possibility that the property of inhibiting diffusion of the donor element or the acceptor element into the semiconductor substrate is increased.

The above carrier is preferably a material exhibiting a Brunauer-Emmett-Teller (BET) specific surface area of 10 m ² /g or more. Such a carrier can be exemplified by particles of an inorganic material such as cerium oxide (SiO ₂ ), activated carbon, carbon fibers, or zinc oxide.

The shape of the particles is not particularly limited, and may be any of a substantially spherical shape, a flat shape, a scale shape, a block shape, an ellipsoid shape, a plate shape, and a rod shape. Above particles The shape can be confirmed by an electron microscope or the like.

The content of the specific metal compound in the barrier layer-forming composition is determined in consideration of application characteristics such as coatability, diffusibility of a donor element or an acceptor element, and the like. In general, the content of the specific metal compound in the barrier layer-forming composition is preferably 0.1% by mass or more and 80% by mass or less, more preferably 1% by mass or more and 60% by mass or less, more preferably 1% by mass or more and 60% by mass or less. It is 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and most preferably 10% by mass or more and 25% by mass or less.

When the content of the specific metal compound is 0.1% by mass or more, diffusion of the donor element or the acceptor element into the semiconductor substrate can be sufficiently inhibited. When the content of the specific metal compound is 80% by mass or less, the dispersibility of the specific metal compound in the barrier layer-forming composition is improved, and the application properties such as the coating property to the substrate are improved.

Further, the total mass ratio of the specific metal compound among all the nonvolatile components of the barrier layer-forming composition is preferably 0.5% by mass or more and less than 95% by mass, more preferably 20% by mass or more and 80% by mass or less, and particularly preferably 60% by mass or more and 80% by mass or less. If it is in the above range, there is a tendency that a sufficient barrier control effect can be obtained.

Here, the non-volatile component means a component that does not volatilize when heat-treated at 600° C. or higher and 1200° C. or lower. Further, the non-volatile component can be obtained by a thermogravimetry (TG), and means that the weight loss rate at 600 ° C to 1200 ° C is 10% by mass or less. In addition, in the non-volatile content The total mass ratio of the specific metal compound can be determined by inductively coupled plasma (ICP) emission spectrochemical analysis/mass spectrometry or atomic absorption method.

(dispersion medium)

The composition for forming a barrier layer of the present invention contains a dispersion medium. The dispersion medium refers to a medium in which the specific metal compound is dispersed or dissolved in the composition. The dispersion medium can be exemplified by a solvent and water.

The above solvent may, for example, be acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone or methyl-n-pentanone. , methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, di-isobutyl ketone, trimethyl fluorenone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentyl Ketone solvents such as diketone and acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl ether, di-isopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyl dioxane , ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl-n-propyl ether, diethylene glycol methyl-n-butyl ether, diethylene glycol di-n-propyl ether, two Diol-n-butyl ether, diethylene glycol methyl-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol Base-n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl-positive Ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methyl ethyl ether, tetraethylene glycol methyl-n-butyl ether, tetraethylene glycol di-n-butyl ether, Tetraethylene glycol methyl-n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol II - n-propyl ether, propylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol di-n-propyl ether, Dipropylene glycol di-n-butyl ether, dipropylene glycol methyl-n-hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl-n-butyl ether, tripropylene glycol - n-butyl ether, tripropylene glycol methyl-n-hexyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, tetrapropylene glycol methyl ethyl ether, tetrapropylene glycol methyl-n-butyl ether, tetrapropylene glycol di-n-butyl Ether solvent such as ether, tetrapropylene glycol methyl-n-hexyl ether or tetrapropylene glycol di-n-butyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate Ester, 2-butyl acetate, n-amyl acetate, 2-pentyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2-(2-Butoxyethoxy)ethyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, decyl acetate , ethyl acetate methyl acetate, ethyl acetate ethyl acetate, diethylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diethyl ether acetate, ethylene Alcohol diacetate, methoxy triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, lactate B Ester, n-butyl lactate, n-amyl lactate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether An ester solvent such as an acid ester, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, γ-butyrolactone or γ-valerolactone; acetonitrile, N-methyl pyrrolidinone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N-hexylpyrrolidone, N-cyclohexylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, Aprotic polar solvent such as dimethyl hydrazine; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, tert-butanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, 2-pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-hexanol, 2-ethylbutanol, 2-glycol Alcohol, n-octanol, 2-ethylhexanol, 2-octanol, n-nonanol, n-nonanol, 2-undecyl alcohol, trimethylnonanol, 2-tetradecyl alcohol, 2- Heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, benzyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol Alcohol, tripropylene glycol and other alcohol solvents; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether (cellosolve), ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triethylene glycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol a glycol monoether solvent such as monoethyl ether or tripropylene glycol monomethyl ether; a polycyclic alcohol solvent such as isobornylcyclohexanol; - terpineol such as ?-terpinene, rosinol such as ?-terpineol, myrcene, allophymene, limonene, dipentene, ? a terpene-based solvent such as a terpene such as a-pinene or β-pinene, a carvone, an ocimene or a phellandrene. These solvents may be used alone or in combination of two or more.

Among these solvents, the dispersion medium is preferably selected from the group consisting of water, an alcohol solvent, a glycol monoether solvent, isobornylcyclohexanol, and a terpene solvent from the viewpoint of application characteristics of the semiconductor substrate. One or more, more preferably selected from the group consisting of water, alcohol, ethylene glycol monoethyl ether, rosinol, diethylene glycol mono-n-butyl ether, and diethylene glycol mono-n-butyl ether More than one type, especially preferably selected from water, alcohol, One or more of the group consisting of rosin and ethylene glycol monoethyl ether.

The content ratio of the dispersion medium in the barrier layer-forming composition is determined in consideration of application characteristics, barrier properties of the barrier layer, and the like. In the composition for forming a barrier layer, the content of the dispersion medium is preferably 5% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 95% by mass or less, and particularly preferably 40% by mass or more and 90% by mass or less.

(thixotropy)

The barrier layer-forming composition of the present invention contains one or more kinds of thixotropic agents. A thixo agent is also called a thixotropic agent, a thixotropic imparting agent, or a thixotropic imparting agent. The thixotropic agent imparts a thixotropy to the composition for forming a barrier layer, and imparts a sol shape when a stress is applied at a fixed temperature, and returns to a gel state once it is placed.

Specifically, for example, when a barrier layer forming composition containing a thixotropic agent is printed on an object (for example, a semiconductor substrate) by a screen printing machine, a scraper or a squeegee operates to contact the barrier layer. When a stress is applied to the composition for forming a barrier layer, the composition for forming a barrier layer has a reduced viscosity and fluidity, and a barrier layer-forming composition is formed on the object by the mesh of the screen. Floor. In addition, as long as the layer of the barrier layer-forming composition temporarily formed on the object is not stressed, the viscosity does not decrease, and the shape can be maintained.

Further, when the barrier layer-forming composition contains a thixotropic agent, for example, when a barrier layer having a fine line-like pattern shape is formed, it can be applied to a semiconductor substrate without causing a pattern shape to be enlarged in the plane direction of the semiconductor substrate. on. and then, The desired pattern shape can also be maintained by removing at least a portion of the dispersion medium by drying or the like. Further, as long as the desired pattern shape can be maintained after drying, the barrier layer can be formed in a specific size in a specific region.

By including a thixotropic agent, it is possible to impart an appropriate shear viscosity to the barrier layer-forming composition and to impart excellent application properties such as printability.

Specifically, the shear viscosity in the range of the shear rate of the barrier layer forming composition of 0.01 [s ^-1 ] to 10 [s ^-1 ] was measured at 25 ° C, and the shear rate was x [s ^-1 ]. The common logarithm of the shear viscosity η ^x is expressed as log ₁₀ (η ^x ), and the thixotropic index (thixotropic index, TI) is calculated at [log ₁₀ (η ^0.01 )-log ₁₀ (η ¹⁰ )]. In the case of a value, the TI value is preferably greater than 1, more preferably greater than 1.3, and even more preferably greater than 1.5.

The upper limit of the above-mentioned TI value is not particularly limited, but the upper limit of the TI value is preferably 4.0 or less from the viewpoint of difficulty in occurrence of blur at the time of formation of the thin line pattern and ease of workability, and more preferably Below 3.5, it is especially preferably 3.0 or less. Further, the shear viscosity of the barrier layer-forming composition can be measured using a viscoelasticity measuring device (for example, manufactured by Anton-Parr Co., Ltd., MCR-301).

The thixotropic agent is not particularly limited as long as the above effects are obtained, and it is preferred to contain one or more selected from the group consisting of polyether compounds, fatty acid guanamines, organic fillers, inorganic fillers, and hydrogenated castor oil. Urea amide amide, biogum, guar gum, Locust bean gum, carrageenan, pectin, agar , β-glucan (β-glucan), tamarind seed gum, psyllium seed gum, polyvinylpyrrolidone, anthrone-based thickening gelling agent And oil gelling agent. Among these thixotropic agents, the thixotropic agent preferably contains a polyether compound, a fatty acid decylamine, an organic filler, an inorganic filler, and a hydrazine hydride from the viewpoints of ease of handling and ease of adjustment of thixotropy. One or more of the group consisting of sesame oil, urea carbamide phthalamide, polyvinylpyrrolidone, anthrone creping gelling agent, and oil gelling agent, and particularly preferably One of the group consisting of a free polyether compound, a fatty acid guanamine, and an inorganic filler is particularly preferably at least one selected from the group consisting of polyether compounds. The thixotropic agent may be used alone or in combination of two or more.

The form of the thixotropic agent is not particularly limited, and it is preferably present as a solid at normal temperature (about 20 ° C). The thixotropic agent exists as a solid and functions as a filler to further improve thixotropy. Therefore, the printing of the fine line pattern shape becomes easier. The melting point of the thixotropic agent is preferably from 40 ° C to 150 ° C.

In the case where the thixotropic agent is a polyether compound, a fatty acid decylamine or a hydrogenated castor oil, it is preferred to carry out heat treatment in a dispersion medium at a temperature exceeding the melting point of the thixotropic agent. The thixotropic agent is temporarily melted, and then cooled to normal temperature for use, whereby the thixotropic agent is uniformly precipitated in the dispersion medium, and the effect of improving thixotropy is further improved.

When the thixotropic agent is solid at a normal temperature and has a particle shape, the volume average particle diameter is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, and particularly preferably 1 μm or less. Preferably, it is 0.1 μm or less. When the volume average particle diameter is 20 μm or less, there is a tendency that thixotropy can be easily applied with a small addition amount. The lower limit of the volume average particle diameter is not particularly limited, and is preferably 10 nm or more. If the lower limit of the volume average particle diameter is 10 nm or more, the barrier layer forming composition is present. The dispersibility of the thixotropic agent tends to be better.

The volume average particle diameter is a measured value (volume distribution) measured by, for example, a laser diffraction/scattering particle size distribution measuring apparatus (manufactured by Horiba, LA-920) and a laser wavelength of 750 nm, as a volume average particle diameter. Calculated by (50% diameter).

In the composition for forming a barrier layer, the content of the thixotropic agent is preferably from 0.01% by mass to 40% by mass, more preferably from 0.1% by mass to 30% by mass, even more preferably from 0.1% by mass to 25% by mass, particularly preferably 1% by mass to 15% by mass, and preferably 2% by mass to 12% by mass. When the content of the polymer compound is 0.01% by mass or more, the application characteristics such as printability tend to be further improved. In addition, when the content is 40% by mass or less, the viscosity does not increase excessively, and the workability in the case of using a printing method such as screen printing tends to be further improved.

The mass ratio of the thixotropic agent to the specific metal compound in the composition for forming a barrier layer (thixotropic agent: specific metal compound) is not particularly limited, and the thixotropic agent and the specific metal are used from the viewpoint of easiness of thixotropy adjustment. The quality of the compound is preferably 0.5:99.5~99:1, more preferably 1:99~90:10, especially preferably 1.5:98.5~80:20, and particularly preferably 2:98~40:60.

The polyether compound is preferably a polyether compound represented by the following formula (1) (hereinafter also referred to simply as a polyether compound).

[Chemical 2]

In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, n represents an integer of 1 or more, and R ² each independently represents an exoethyl group (C ₂ H ₄ ) or a propylene group. Base (C ₃ H ₆ ).

The combination of R ¹ and R ³ is not particularly limited, and it is preferred that any of R ¹ and R ³ is a hydrogen atom, and it is more preferred that both R ¹ and R ³ are a hydrogen atom. When both R ¹ and R ³ are a hydrogen atom, there is a tendency that the solubility in the dispersion medium is more easily controlled. Therefore, when the composition for forming a barrier layer is used to form a fine-line pattern shape, it is possible to apply to the semiconductor substrate while suppressing the growth of the pattern shape more effectively, and to remove at least a part of the dispersion medium by drying or the like. After that, the desired pattern shape can be maintained. The barrier layer can be formed in a specific size in a specific region as long as the desired pattern shape can be maintained after drying.

Further, the upper limit of n is not limited, and is preferably 10,000 or less.

Specific examples of the polyether compound include polyethylene glycol, polypropylene glycol, and poly(ethylene glycol-propylene glycol) copolymer. The poly(ethylene glycol-propylene glycol) copolymer may be a random copolymer or a block copolymer.

Among them, it is preferred to contain one or more selected from the group consisting of polyethylene glycol and polypropylene glycol. By using one or more selected from the group consisting of polyethylene glycol and polypropylene glycol, there is application such as printability of a barrier layer-forming composition. The tendency to improve characteristics. In addition, these polyether compounds are also easy to handle. Further, the polyether compound can be used by mixing and copolymerizing two or more kinds of polyether compounds having different structures.

The number average molecular weight of the polyether compound is preferably from 300 to 5,000,000, more preferably from 1,000 to 100,000, particularly preferably from 10,000 to 50,000. When the number average molecular weight is 300 or more, the function as a filler can be sufficiently obtained, and the application characteristics such as printability tend to be further improved. When the number average molecular weight is 5,000,000 or less, it is possible to suppress an excessive increase in viscosity, and thus the application characteristics such as printability tend to be further improved. The number average molecular weight can be determined using a gel permeation chromatograph (GPC). Further, the measurement conditions of the number average molecular weight obtained by the GPC method are as follows, for example.

Measuring device: Shodex GPC SYSTEM-11 (manufactured by Showa Denko)

Lysate: CF ₃ COONa 5 mmol / hexafluoroisopropanol (HFIP) (1 L)

Column: sample column HFIP-800P, HFIP-80M × 2, reference column HFIP-800R × 2

Column temperature: 40 ° C

Flow rate: 1.0 ml/min

Detector: Shodex RI STD: PMMA (Shodex STANDARD M-75)

The fatty acid guanamine may be exemplified by the fatty acid represented by the formula (2). The guanamine, the N-substituted fatty acid decylamine represented by the formula (3) or the formula (4), and the N-substituted fatty acid guanamine represented by the formula (5).

R ⁴ CONH ₂ ......(2)

R ⁴ CONH-R ⁵ -NHCOR ⁴ ......(3)

R ⁴ NHCO-R ⁵ -CONHR ⁴ ......(4)

R ⁴ CONH-R ⁵ -NR ⁶ R ⁶ ......(5)

In the general formula (2), the general formula (3), the general formula (4), and the general formula (5), R ⁴ and R ⁶ each independently represent an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and R ⁵ represents carbon. The number of alkyl groups of 1 to 10; R ⁴ and R ⁶ may be the same or different.

In the general formula (2), the general formula (3), the general formula (4), and the general formula (5), the alkyl group and the alkenyl group represented by R ⁴ and R ⁶ are each independently a carbon number of 1 to 30. The alkyl group and the alkenyl group represented by R ⁴ are each independently preferably a carbon number of 5 to 25, more preferably a carbon number of 10 to 20, and particularly preferably a carbon number of 15 to 18. The alkyl group and the alkenyl group represented by R ⁶ are each independently preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 3.

The alkyl group and the alkenyl group having 1 to 30 carbon atoms represented by R ⁴ and R ⁶ may each independently be linear, branched or cyclic, and are preferably linear or branched.

R ^{5 is} preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably having a carbon number of 1 to 3 carbon atoms. Alkyl.

Specifically, examples of the alkyl group and the alkenyl group having 1 to 30 carbon atoms represented by R ⁴ and R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a decyl group, and a tenth group. Dialkyl, octadecyl, hexadecenyl, behenyl and the like.

Further, the alkyl group and the alkenyl group having 1 to 30 carbon atoms represented by R ⁴ and R ⁶ may be unsubstituted or may have a substituent. Examples of such a substituent include a hydroxyl group, a chlorine group, a bromine group, a fluorine group, an aldehyde group, a carbonyl group, a nitro group, an amine group, a sulfonic acid group, an alkoxy group, a decyloxy group and the like.

In the general formula (3), the general formula (4), and the general formula (5), the alkylene groups represented by R ⁵ are each independently a carbon number of 1 to 10, preferably a carbon number of 1 to 8, more preferably carbon. The number is 1~6, especially the carbon number is 1~4.

Specifically, the alkylene group having 1 to 10 carbon atoms represented by R ² may, for example, be an extended ethyl group, a stretched propyl group, a butyl group or a decyl group.

Specific examples of the fatty acid monodecylamine represented by the formula (2) include decyl laurate, decyl palmitate, decylamine stearate, decyl oleate, and decyl erucamide.

Further, specific examples of the N-substituted fatty acid decylamine represented by the formula (3) include N,N'-extended ethyl bislaurate decylamine and N,N'-methylenebisstearate decylamine. , N, N'-extended ethyl bis-stearate decylamine, N, N'-extended ethyl bis-oleic acid decylamine, N, N'-extended ethyl bis-decanoic acid decylamine, N, N'- Ethyl bis- 12-hydroxystearic acid decylamine, N,N'-butyl-butyl bis-stearate, amide, N,N'-hexamethylenebisstearate, N,N'- Hexamethylene bis-oleic acid decylamine, N,N'-phthalic dimethyl stearate and the like.

Further, specific examples of the N-substituted fatty acid decylamine represented by the general formula (4) include N,N'-dioleyl adipic acid decylamine and N,N'-distearoyl adipate decylamine. , N, N'-dioleyl sebacate, N, N'-distearoyl sebacate, N, N'- distearyl terephthalate, N, N' - distearyl phthalamide and the like.

Further, specific examples of the N-substituted fatty acid guanamine represented by the formula (5) Examples thereof include dimethylaminopropyl decylamine stearate, diethylaminoethyl decylamine stearate, dimethylaminopropyl decyl laurate, and dimethylaminol myristate. Propyl decylamine, dimethylaminopropyl decylamine palmitate, dimethylaminopropyl decylamine stearate, dimethylaminopropyl decyl amide, dimethylamino oleate Propyl decylamine, dimethylaminopropyl decylamine isostearate, dimethylaminopropyl decyl linolenate, dimethylaminopropyl decylamine ricinoleate, hydroxystearic acid Methylaminopropyl decylamine, N,N-bishydroxymethylaminopropyl decylamine stearate, diethylaminoethyl guanamine laurate, diethylaminoethyl hydrazide Amine, diethylaminoethyl palmitate, diethylaminoethylguanamine stearate, diethylaminoethylguanamine behenate, diethylaminoethyl oleate Amine, linolenic acid diethylaminoethyl decylamine, ricinoleic acid diethylaminoethyl decylamine, isostearic acid diethylaminoethyl decylamine, hydroxystearic acid diethylamine Ethyl decylamine, N,N-bishydroxyethylaminoethylguanamine Diethylaminopropyl laurate laurate, diethylaminopropyl decyl myristate, diethylaminopropyl decyl palmitate, diethylaminopropyl decylamine stearate, Diethylaminopropyl decylamine behenate, diethylaminopropyl decylamine oleate, diethylaminopropyl decyl linolenate, diethylaminopropyl decyl ricinoleate , diethylaminopropyl decylamine isostearate, diethylaminopropyl hydroxy hydroxystearate, N, N-bishydroxyethylaminopropyl decylamine and the like.

Among these fatty acid decylamines, from the viewpoint of solubility in a dispersion medium, it is preferably selected from the group consisting of a fatty acid monodecylamine represented by the general formula (2) and an N-substituted fatty acid decylamine represented by the general formula (3). And one or more of the group consisting of the N-substituted fatty acid amide amine represented by the formula (5), more preferably one or more selected from the group consisting of the following compounds: R ⁴ is a carbon number An alkyl or alkenyl group of 10 to 20, R ⁵ is an alkylene group having 1 to 30 carbon atoms, and R ⁶ is an alkyl group having 1 to 6 carbon atoms or an alkenyl group, and the fatty acid monodecylamine represented by the formula (2) The N-substituted fatty acid decylamine represented by the formula (3) and the N-substituted fatty acid guanamine represented by the formula (5).

Further, among these fatty acid decylamines, from the viewpoint of solubility in a dispersion medium, it is preferably selected from decylamine stearate, decylamine N,N'-methylenebisstearate, and stearic acid One or more of the groups consisting of methylaminopropyl decylamine, more preferably selected from the group consisting of decylamine stearate and decylamine N,N'-methylenebisstearate One or more.

The fatty acid guanamine is preferably evaporated or decomposed below 400 ° C, more preferably evatilized or decomposed below 300 ° C, and more preferably evacuated or decomposed below 250 ° C.

The lower limit of the temperature at which the fatty acid oxime is evaluated or decomposed is not particularly limited, but is preferably 80° C. or higher, and more preferably 100° C. or higher from the viewpoint of suppressing pattern sag during heat treatment after pattern formation. Especially preferred is above 150 °C. The evapotranspiration or decomposition temperature of the fatty acid guanamine was measured by using a thermogravimetric analyzer to investigate the temperature at which the weight retention ratio was 20% or less.

In the case where the composition for forming a barrier layer contains a fatty acid decylamine as a thixotropic agent, the content of the fatty acid guanamine is preferably from 1 part by mass to 30 parts by mass, more preferably 100 parts by mass of the barrier layer-forming composition. It is preferably 3 parts by mass to 25 parts by mass, particularly preferably 5 parts by mass to 20 parts by mass. By setting the content of the fatty acid decylamine to 1 part by mass to 30 parts by mass based on 100 parts by mass of the barrier layer-forming composition, high thixotropy can be imparted to the barrier layer-forming composition.

The inorganic filler can be exemplified by silica (silicon oxide), clay, tantalum carbide, tantalum nitride, montmorillonite, bentonite, carbon black. Among these inorganic fillers, it is preferred to use a filler containing cerium oxide as a component. Here, the term "clay" means a layered clay mineral, and specific examples thereof include kaolinite, imagolite, montmorillonite, smectite, sericite, and y. Illite, talc, stevensite, zeolite, and the like.

By adding an inorganic filler as a thixotropic agent, it is possible to suppress the bleeding of the paste in the step of applying and drying the barrier layer-forming composition and the hypertrophy of the pattern shape in the surface direction of the semiconductor substrate due to the occurrence of heat sag. With regard to the bleeding generated at the time of application, the bleeding caused by the dispersion medium is suppressed by the interaction of the dispersion medium with the inorganic filler.

The BET specific surface area of the inorganic filler is preferably from 1 m ² /g to 300 m ² /g, particularly preferably from 10 m ² /g to 200 m ² /g. It is preferred to use fumed silica in the inorganic filler. The so-called smoked cerium oxide refers to ultrafine particles (BET specific surface area of 30 m ² /g to 500 m ² /g) of anhydrous cerium oxide, which is a cerium such as cerium tetrachloride in the flame of oxygen and hydrogen. Hydrolyzed to make. Since it is synthesized by a vapor phase method, the primary particle diameter becomes small, and the BET specific surface area becomes large. By using an inorganic filler having a high BET specific surface area, there is a physical interaction between a dispersion medium (solvent) having a reduced viscosity in a drying step, and an interaction caused by a van der Waals force. It is easy to suppress the tendency of viscosity to decrease. The BET specific surface area can be calculated from the adsorption isotherm of nitrogen at -196 °C. For example, it can be measured using BELSORP (manufactured by Bel Japan Co., Ltd.).

The smoked cerium oxide may be hydrophilic or hydrophobic, and may be any one, but it is preferred to use hydrophobic smoked cerium oxide. As a method of being hydrophobic, the surface of the anhydrous cerium oxide can be immersed, sprayed, or the like by using a decane coupling agent having an organic functional group such as a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group. Surface treatment, and become hydrophobic. Here, the fact that the smoked cerium oxide is hydrophobic is a case where the floating amount becomes 0% in the degree of hydrophobicization obtained by the method of measuring the ratio of the water to the methanol to measure the floating ratio of the powder with respect to the solution. The methanol concentration is 30% by volume or more.

When the composition for forming a barrier layer contains an inorganic filler as a thixotropic agent, the content of the inorganic filler in the barrier layer-forming composition is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass. 10% by mass, particularly preferably 0.5% by mass to 3% by mass. When the content ratio is 0.01% by mass or more, the effect of suppressing heat sag during the drying step tends to be sufficiently obtained. When the content is 20% by mass or less, the application characteristics of the barrier layer-forming composition (fine line formation property, bleed out during printing, heat stagnation during heat drying, and the like) tend to be ensured.

In the case where the barrier layer-forming composition contains an inorganic filler as a thixotropic agent, the inorganic filler is preferably dispersed in the dispersion medium. The method of dispersing the inorganic filler is not particularly limited, and in the case where the inorganic filler is dissolved in the dispersion medium contained in the composition for forming a barrier layer, it is not necessary to disperse particularly. Insoluble in inorganic fillers In the case of dissolving in the above dispersion medium, it is preferred to use an ultrasonic dispersion, a bead mill, a ball mill, a homogenizer, a sand mill, a roll, a kneader, a dissolver ( Dissolve), stirring wings, etc. to disperse.

The organic filler refers to a particulate or fibrous filler containing an organic compound. The organic compound constituting the organic filler may be appropriately selected from the group consisting of urea formalin resin, phenol resin, polycarbonate resin, melamine resin, epoxy resin, unsaturated polyester resin, Anthrone resin, polyurethane resin, polyolefin resin, acrylic resin, fluororesin, polystyrene resin, cellulose, formaldehyde resin, coumarone-indene resin, lignin , petroleum resin, amine based resin, polyester resin, polyether oxime resin, butadiene resin, copolymer of these resins, and the like. These resins may be used alone or in combination of two or more.

Among these compounds, the organic filler is preferably a compound which decomposes at 700 ° C or lower. Since the organic filler is a compound which decomposes at 700 ° C or lower, it is possible to sufficiently suppress the organic filler from becoming a residue after forming the impurity diffusion layer by heat.

The organic filler is more preferably a compound which decomposes at 400 ° C or lower, and particularly preferably has a temperature of 300 ° C or less. The lower limit of the decomposition temperature is not particularly limited, but is preferably 150° C. or higher, and more preferably 200° C. or higher from the viewpoint of workability in the coating step.

The decomposition temperature referred to herein means a temperature at which an organic filler disappears by heat. The decomposition temperature can be measured by a thermogravimetric analyzer (Shimadzu Corporation, DTG-60H).

From the viewpoint of thermal decomposition, the organic filler is preferably selected from the group consisting of acrylic acid. One or more of the group consisting of a resin, a cellulose resin, and a polystyrene resin is more preferably an acrylic resin.

Further, examples of the monomer constituting the acrylic resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, and isopropyl acrylate. Isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-butyl acrylate, 2-butyl methacrylate, tert-butyl acrylate , butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid 2-ethylhexyl ester, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecane methacrylate Base ester, tetradecyl acrylate, tetradecyl methacrylate, cetyl acrylate, cetyl methacrylate, octadecyl acrylate, octadecyl methacrylate ,acrylic acid Decaalkyl ester, eicosyl methacrylate, behenyl acrylate, behenyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, A Cyclohexyl acrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methoxy methacrylate Ethyl ethyl ester, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylamino acrylate Propyl ester, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate Ester, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, dicyclopentyl methacrylate, dicyclopentanyl acrylate, and the like. Further, monomers constituting the acrylic resin may be used in combination: styrene, α-methylstyrene, cyclohexylmethyleneimine, vinyl toluene, vinyl chloride, vinyl acetate, N-vinylpyrrolidone Butadiene, isoprene, chloroprene, and the like. These monomers may be used alone or in combination of two or more.

The particle diameter of the organic filler is preferably 10 μm or less, more preferably 1 μm or less, and particularly preferably 0.1 μm or less. When the particle diameter is 10 μm or less, precipitation is less likely to occur, and clogging is less likely to occur.

The molecular weight of the organic compound used as the organic filler is not particularly limited, and may be appropriately adjusted depending on the desired viscosity, thixotropy or the like as a composition.

When the barrier layer-forming composition contains an organic filler as a thixotropic agent, the content of the organic filler in the barrier layer-forming composition is preferably from 0.01% by mass to 20% by mass, more preferably from 0.1% by mass to 10% by mass. The mass% is particularly preferably 0.5% by mass to 3% by mass. When the content ratio is 0.01% by mass or more, the effect of suppressing heat sag during the drying step tends to be sufficiently obtained. When the content is 20% by mass or less, the application characteristics of the barrier layer-forming composition (fine line formation property, bleed out during printing, heat stagnation during heat drying, and the like) tend to be ensured.

Bioglue can be exemplified by gellan gum, xanthan, curdlan, pullulan, dextran, and rhamsan gum. , Welan gum.

The anthrone-based tackifying gelling agent may be exemplified by an amino acid-modified fluorenone, a polyamido-fluorenone alternating copolymer, a side chain alkyl-modified fluorenone, a side chain polyether modified fluorenone, The two-terminal alkyl modified fluorenone, the fluorenone modified polytriglucose, and the fluorenone modified acrylic acid.

The hydrogenated castor oil-based thixotropic agent is exemplified by Disparlon 308 (manufactured by Nanben Chemical Co., Ltd.). The urea urethane phthalamide is exemplified by BYK-410 manufactured by BYK-Chemie Japan. The oil gelling agent is exemplified by GEL ALL (manufactured by Shin-Nippon Chemical Co., Ltd.). Examples of the polyvinylpyrrolidone include those having a weight average molecular weight of 3,000 to 5,000,000.

The combination in the case where two or more kinds of thixotropic agents are used in combination is not particularly limited. The combination of the thixotropic agent may be a combination of polyethylene glycol and a hydrogenated castor oil-based thixotropic agent, a combination of polyethylene glycol and urea urethane decylamine, a combination of decyl stearate and an inorganic filler. A combination of polyethylene glycol and an inorganic filler.

Preferably, the barrier layer-forming composition comprises: a metal compound containing an alkaline earth metal or an alkali metal, the metal compound being selected from the group consisting of metal oxides, metal carbonates, metal nitrates, metal sulfates, and metal hydroxides. One or more kinds of the group; the dispersion medium which is one or more selected from the group consisting of water, an alcohol solvent, a glycol monoether solvent, and a terpene solvent; and a thixotropic agent selected from the group consisting of Polyether compound, fatty acid decylamine, organic filler, inorganic filler, hydrogenated castor oil, urea amide decylamine, polyvinylpyrrolidone, anthrone cresifying gelling agent and oil gelling agent One or more of the group consisting of; and containing alkaline earth metals The content of the alkali metal compound is 0.1% by mass or more and 80% by mass or less, and the TI value is more than 1.3 and 4.0 or less.

Further, the barrier layer forming composition is more preferably comprising: a metal compound containing an alkaline earth metal or an alkali metal selected from the group consisting of metal oxides, metal carbonates, metal nitrates, metal sulfates, and metal hydroxides. One or more of the group consisting of: a dispersion medium selected from the group consisting of water, an alcohol solvent, a glycol monoether solvent, and a terpene solvent; and a thixotropic agent, which is Free polyether compound, fatty acid decylamine, organic filler, inorganic filler, hydrogenated castor oil, urea amide decylamine, polyvinylpyrrolidone, fluorenone visifying gelling agent and oil gel One or more of the group consisting of the chemical agent; and the metal compound containing an alkaline earth metal or an alkali metal has a particle diameter of 0.01 μm to 30 μm, a content of 0.1% by mass or more and 80% by mass or less, and a TI value of more than 1.3 and below 4.0.

(other ingredients)

The barrier layer-forming composition may further contain various additives such as an organic binder, a tackifier, a wetting agent, a surfactant, and a resin containing a ruthenium atom, in addition to a specific metal compound, a dispersion medium, and a thixotropic agent. Come as other ingredients.

When the composition for forming a barrier layer contains an organic binder, it is easy to bond specific metal compounds to each other by using an organic binder at a high temperature, and it is easy to bond a specific metal compound to a semiconductor substrate.

Examples of the organic binder include: polyvinyl alcohol; polypropylene decylamine resin; polyethyl acrylate Alkenyl decylamine resin; polyvinylpyrrolidone resin; polyethylene oxide resin; polyfluorene resin; acrylamide alkyl hydrazine resin; cellulose ether, carboxymethyl cellulose, hydroxyethyl cellulose, Cellulose resin such as cellulose; gelatin and gelatin derivatives; starch and starch derivatives; sodium alginate; Sanxian gum and Sanxian gum derivatives; guar gum and guar gum derivatives; Hard glucan derivatives; tragacanth and xanthan gum derivatives; dextrin and dextrin derivatives; (meth)acrylic resin, alkyl (meth)acrylate resin, (a (meth)acrylic resin such as dimethylaminoethyl acrylate resin; butadiene resin; styrene resin; butyraldehyde resin; and copolymer of these compounds.

Among the above-mentioned organic binders, from the viewpoint of decomposability and prevention of liquid sag during screen printing, it is preferred to include a group selected from the group consisting of (meth)acrylic resins, cellulose resins, and butyral resins. One or more. The organic binder may be used alone or in combination of two or more.

The molecular weight of the organic binder is not particularly limited and can be appropriately adjusted depending on the desired viscosity as a composition.

In the case where the organic binder is contained, the content of the organic binder is preferably 0.5% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, more preferably 3% by mass or more and 25% by mass or less. It is 3% by mass or more and 20% by mass or less.

In the case where the barrier layer-forming composition contains an organic binder, the mass ratio of the total content of the specific metal compound in the barrier layer-forming composition to the total content of the organic binder (specific metal compound) / (organic binder) Preferably 99.9/0.1 ~0.1/99.9, more preferably 99/1~20/80.

Further, a dispersion medium in which an organic binder is dissolved may be used as the dispersion medium and the organic binder.

Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and the like. Among them, a nonionic surfactant or a cationic surfactant is preferred in that the amount of impurities such as heavy metals introduced into the semiconductor element is small. Further, an anthrone-based surfactant, a fluorine-based surfactant, or a hydrocarbon-based surfactant can be exemplified as the nonionic surfactant. In terms of rapid disappearance upon heating such as diffusion, a hydrocarbon-based surfactant is preferred.

The hydrocarbon-based surfactant may, for example, be a block copolymer of ethylene oxide-propylene oxide or an acetylenic glycol compound, and is more preferably capable of more uniformly blocking the diffusion of the impurity element. It is an acetylene glycol compound.

The inorganic powder may, for example, be a powder of tantalum nitride, cerium oxide, cerium carbide or the like.

The barrier layer-forming composition of the present invention does not contaminate the semiconductor substrate, that is, the composition for forming a barrier layer, iron, tungsten, gold, nickel, chromium, The content of manganese or the like is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.

The viscosity of the composition for forming a barrier layer is not particularly limited. Specifically, the viscosity measured by an E-type viscometer at a rotational speed of 0.5 rpm to 5 rpm at 25 ° C is preferably 0.5 Pa. s~400 Pa. s, more preferably 10 Pa. s~100 Pa. s. If the above viscosity is 0.5 Pa. Above s, it is difficult to cause liquid sag when applied to a semiconductor substrate, and if the viscosity is 400 Pa. Below s, a fine pattern can be formed.

Further, the viscosity of the composition for forming a barrier layer can be determined by a rotation method, a stress control method, or a strain control method using a B-type viscometer, an E-type viscometer, a viscoelasticity measuring device, or the like.

The barrier layer-forming composition of the present invention can be obtained by mixing a specific metal compound, a dispersion medium, a thixotropic agent, and optionally a component, by using a blender, a mixer, a mortar, and a rotor. In addition, heating may be performed as needed. The heating temperature at this time can be, for example, 30 ° C to 100 ° C.

<Semiconductor substrate with barrier layer>

The semiconductor substrate with a barrier layer of the present invention includes a semiconductor substrate and a barrier layer obtained by removing at least a portion of the dispersion medium from the composition for forming a barrier layer applied to the semiconductor substrate. By providing the barrier layer on the semiconductor substrate, the impurity diffusion layer can be selectively formed in a region other than the region in which the barrier layer is provided.

The amount of application of the barrier layer-forming composition to the semiconductor substrate is not particularly limited, but is preferably 0.01 g/m ² to 100 g/m ² , more preferably 0.1 g/m ² to 20 g/m ² . The thickness of the barrier layer formed by applying the composition for forming a barrier layer is not particularly limited, but is preferably 0.1 μm to 50 μm, more preferably 1 μm to 30 μm.

Further, the barrier layer is formed by removing at least a part of the dispersion medium contained in the barrier layer forming composition. Examples of the method for removing the dispersion medium include a heat treatment for 1 minute to 10 minutes when a hot plate is used at a temperature of about 80 ° C to 500 ° C, and a time of about 10 minutes to 30 minutes when a dryer or the like is used. Heat treatment. The heat treatment condition depends on the component of the barrier layer forming composition The type and content of the bulk medium are not particularly limited to the above conditions in the present invention.

The content rate (residual ratio) of the dispersion medium in the barrier layer is not particularly limited. The content of the dispersion medium in the barrier layer is preferably 30% by mass or less, more preferably 0.01% by mass to 15% by mass, even more preferably 0.1% by mass to 5% by mass. The content of the dispersion medium in the barrier layer can be calculated from the content of the nonvolatile component in the barrier layer-forming composition and the amount of the barrier layer-forming composition applied to the semiconductor substrate.

<Method for Manufacturing Solar Cell Substrate and Solar Cell Element>

The method for producing a substrate for a solar cell according to the present invention includes the step of applying a composition for forming a barrier layer on a semiconductor substrate to form a barrier layer on a semiconductor substrate, and forming a donor element or an acceptor element from the semiconductor substrate. The step of partially forming the impurity layer and not forming the impurity diffusion layer in the semiconductor substrate partially forms an impurity diffusion layer.

Moreover, the method for producing a solar cell element of the present invention includes the step of forming an electrode on the impurity diffusion layer of the solar cell substrate obtained by the above-described production method.

Here, a solar cell substrate and a method for producing a solar cell element using the composition for forming a barrier layer of the present invention will be described with reference to FIG. 1 . FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing procedure of a solar cell substrate and a solar cell element according to the present invention.

In addition, although the back electrode type solar cell substrate and the solar cell element are described in FIG. 1, the barrier layer forming composition of the present invention can be applied to other types of solar cell substrates and solar cell elements.

Other examples of the back electrode type include a selective emitter type, a double-sided light receiving type solar cell substrate, and a solar cell element. In the selective emitter type, a diffusion layer having a higher impurity concentration than other regions is formed directly under the electrode on the light-receiving surface side. In order to form a region of the high concentration diffusion layer, the composition for forming a barrier layer of the present invention can be used. Further, in the double-sided light receiving type, a finger bar and a bus bar are formed as electrodes on both sides, and an n ⁺ -type diffusion layer is formed on one side of the semiconductor substrate, and p ⁺ is formed on the other side ^. Type diffusion layer. In order to selectively form the n ⁺ -type diffusion layer and the p ⁺ -type diffusion layer in position, the barrier layer-forming composition of the present invention can be used.

In (1) of FIG. 1, an alkali solution is applied onto a tantalum substrate as the n-type semiconductor substrate 10 to remove the damaged layer, and a texture structure is obtained on the light-receiving surface side by etching.

Specifically, 20% by mass of caustic soda is used to remove the damaged layer on the surface of the crucible substrate generated from the ingot slicing. Then, etching was carried out by using a mixed solution of 1% by mass of caustic soda and 10% by mass of isopropyl alcohol to form a texture structure (the description of the texture structure is omitted in the drawing). The solar cell element forms a texture structure on the light-receiving surface (surface) side of the ruthenium substrate, thereby promoting the optical confinement effect and achieving high efficiency.

In (2) of FIG. 1, the barrier layer-forming composition 11 of the present invention is applied to the surface (i.e., the light-receiving surface) of the n-type semiconductor substrate 10 and the back surface opposite to the light-receiving surface. In the present invention, the application method is not particularly limited, and examples thereof include a printing method such as screen printing, a spinning method, a brushing method, a spraying method, a doctor blade method, a roll coating method, an inkjet method, and the like, and it is preferred to use a printing method or an inkjet method. law.

The application amount of the barrier layer-forming composition is not particularly limited, but is preferably 0.01 g/m ² to 100 g/m ² , more preferably 0.1 g/m ² to 20 g/m ² . The thickness of the layer formed by applying the above-described composition for forming a barrier layer is not particularly limited, but is preferably 0.1 μm to 50 μm, more preferably 1 μm to 30 μm.

Further, depending on the composition of the composition for forming a barrier layer, a drying step for volatilizing the dispersion medium contained in the composition may be required after the application. In this case, it is dried for 1 minute to 10 minutes when using a hot plate at a temperature of about 80 ° C to 500 ° C, and dried for about 10 minutes to 30 minutes when using a dryer or the like. The drying conditions depend on the type and content of the dispersion medium of the barrier layer-forming composition, and are not particularly limited to the above conditions in the present invention.

The line width of the thin line obtained by applying the barrier layer forming composition preferably has a difference of less than 50 μm, more preferably 40 μm or less, and even more preferably 30 μm or less.

For example, when the composition for forming a barrier layer is applied to a semiconductor substrate to have a line shape of 150 μm in width, the width of the barrier layer-forming composition layer measured after drying is preferably less than 200 μm, more preferably It is 190 μm or less, and particularly preferably 180 μm or less.

Further, the rate of increase in the line width of the fine line obtained by applying the composition for forming a barrier layer is preferably within 150% of the desired set value, more preferably within 140%, and even more preferably within 130%.

Further, in the case of a printing method, an inkjet method, or the like, the pattern-shaped barrier layer is obtained by applying the barrier layer-forming composition 11 to a pattern. On the other hand, in the case of a spinning method, a brushing method, a spraying method, a doctor blade method, a roll coating method, etc., a pattern-like shape The barrier layer is obtained by applying the barrier layer-forming composition 11 to the entire surface and then partially removing it by etching or the like.

Then, in (3) of FIG. 1, the coating diffusion material 12 and the coating diffusion material 13 for forming the n ⁺ -type diffusion layer and the p ⁺ -type diffusion layer are respectively applied. Then, in (4) of FIG. 1, thermal diffusion is performed to form the n ⁺ -type diffusion layer 14 and the p ⁺ -type diffusion layer 15. By the heat treatment for thermal diffusion, the coating diffusion material 12 and the coating diffusion material 13 become the calcined product 12' of the coating diffusion material and the calcined product 13' of the coating diffusion material, and a glass layer is usually formed. The heat treatment temperature for thermal diffusion is not particularly limited, and it is preferably heat-treated at a temperature of 750 ° C to 1050 ° C for 1 minute to 300 minutes.

Here, a method of simultaneously forming an n ⁺ -type diffusion layer and a p ⁺ -type diffusion layer is illustrated, but it may be separately diffused. That is, the coating diffusion material 13 for forming the p ⁺ -type diffusion layer may be first coated, thermally diffused, the burned material 13' of the coating diffusion material may be removed, and then coated for formation of n ⁺ -type diffusion. The coating diffusion material 12 of the layer is thermally diffused to remove the burned material 12' of the diffusion material for coating.

In addition, although the case where the coating diffusion material 12 and the coating diffusion material 13 were used has been described here, the method of using POCl ₃ gas or BBr ₃ gas can also be applied similarly. In this case, first, a barrier layer is formed on the n-type semiconductor substrate 10 in a region other than a predetermined region (opening) where the p ⁺ -type diffusion layer is formed, and the barrier layer forming composition is used, and the BBr ₃ gas is used. After the p ⁺ -type diffusion layer is formed in the region of the n-type semiconductor substrate 10 corresponding to the opening, the barrier layer is removed. Then, a barrier layer is formed by using a barrier layer forming composition in a region other than a predetermined region (opening) where the n ⁺ -type diffusion layer is formed, and the n-type semiconductor substrate 10 corresponding to the opening portion is formed using POCl ₃ gas. The region forms an n ⁺ -type diffusion layer.

Then, in the (5) of FIG. 1 , the barrier layer-forming composition 11 and the burned material 12 ′ of the coating diffusion material and the calcined product 13 ′ of the coating diffusion material are removed to obtain a solar cell substrate. The above-mentioned removal method is exemplified by a method of immersing in an aqueous solution containing an acid, and preferably a composition for forming a barrier layer forming layer 11 and a coating diffusion material for forming an n ⁺ -type diffusion layer and a p ⁺ -type diffusion layer. 12' is determined by the composition of the calcined product 13' of the diffusion material for coating. Specifically, it is preferable to include a step of etching and removing the glass layer formed on the semiconductor substrate by thermal diffusion treatment using an aqueous solution containing hydrofluoric acid. More specifically, a method in which a specific metal compound is removed by hydrochloric acid (for example, 10% by mass aqueous HCl solution), followed by washing with water, and further using a hydrofluoric acid aqueous solution (for example, a 2.5% by mass aqueous HF solution) is used. The calcined product 12' of the coating diffusion material formed on the semiconductor substrate by thermal diffusion treatment and the burned material 13' of the coating diffusion material are removed by etching, and then washed with water.

Then, in (6) of Fig. 1, the anti-reflection film 16 is applied to the surface as the light-receiving surface, and the passivation film 17 is applied on the back side. The composition of the anti-reflection film 16 and the passivation film 17 may be the same or different. The anti-reflection film 16 is, for example, a tantalum nitride film, and the passivation film 17 is a hafnium oxide film. The film thickness of the antireflection film 16 and the passivation film 17 is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm.

Then, in (7) of Fig. 1, the portion where the electrode is formed is opened on the passivation film 17. There is no particular limitation on the method of opening. For example, using an inkjet method or the like, An etchant (for example, a solution containing hydrofluoric acid, ammonium fluoride or phosphoric acid) is applied to the portion to be opened, and heat treatment is performed, whereby the opening can be performed.

Then, in (8) of FIG. 1, the n-electrode 18 and the p-electrode 19 are formed on the n ⁺ -type diffusion layer 14 and the p ⁺ -type diffusion layer 15, respectively. In the present invention, the material and formation method of the electrode 18 and the electrode 19 are not particularly limited. For example, an electrode forming paste containing a metal such as aluminum, silver, or copper can be applied and dried to form the electrode 18 and the electrode 19. Then, the electrode 18 and the electrode 19 are fired to form a solar cell element.

Further, when a glass frit is used as the electrode forming paste, the step of the opening shown in (7) of FIG. 1 can be omitted. When the paste for electrode formation containing glass frit is applied to the passivation film 17, and calcined in the range of 600 ° C to 900 ° C for several seconds to several minutes, the glass frit melts the passivation film 17 on the back side, and the metal particles in the paste (for example) The silver particles form a contact portion with the tantalum substrate 10 to be solidified. Thereby, the formed electrode 18 and the electrode 19 are electrically connected to the ruthenium substrate 10. This is called fire through.

Solar battery

The solar cell includes one or more types of the solar cell elements described above, and is configured by disposing a wiring material on the electrodes of the solar cell element. The solar cell may further connect a plurality of solar cell elements via a wiring material as needed, and further seal with a sealing material. The wiring material and the sealing material are not particularly limited, and may be appropriately selected from materials commonly used in the industry.

[Examples]

Hereinafter, embodiments of the present invention will be further specifically described, but the present invention It is not limited to these embodiments. Further, as long as there is no special description, the reagents are all used in the chemicals. In addition, "%" means "% by mass" unless otherwise specified.

Further, the volume average particle diameter of the specific metal compound in the examples was measured by a laser diffraction scattering particle size distribution measuring apparatus (manufactured by Beckman Coulter, LS 13 320), and the particles were measured in a dispersed state. path.

<Example 1>

(Preparation of composition 1 for barrier layer formation)

Ethyl cellulose (manufactured by Nippon Evol. Co., Ltd., Ethocel STD200, ethylation rate: 50%) 4 g, polyethylene glycol (quantitative molecular weight: 20,000, manufactured by Wako Pure Chemical Industries, Ltd.) 2 g was added to 44 g of rosinol (Nippon Terpene Chemical Co., Ltd.), dissolved at 160 ° C for 1 hour, and then allowed to cool to room temperature. Then, 20 g of calcium carbonate (manufactured by High Purity Chemical Research Co., Ltd., volume average particle diameter of 2.0 μm, amorphous particles) and 30 g of rosin alcohol were added, and mixed in an agate mortar for 5 minutes to prepare a barrier layer. Composition 1.

(Evaluation of thixotropy of the composition for forming a barrier layer)

The thixotropy of the barrier layer-forming composition was measured using a viscoelasticity measuring apparatus (manufactured by Anton-Parr, MCR-301) at a shear rate of 0.01 [s ^-1 ] to 10 [s ^- at 25 ° C. The shear viscosity of the range of ¹ ]. In addition, the common logarithm of the shear viscosity η ^x when the shear rate is x [s ^-1 ] is expressed as log ₁₀ (η ^x ), and the TI value indicating thixotropy is taken as [log ₁₀ (η ^0.01 )-log ₁₀ (η ¹⁰ )] to calculate. The results are shown in Table 1.

(Measurement of printing width)

Use a mask version with a 150 μm line width and use screen printing The machine (MT-320T, manufactured by Microtek Co., Ltd.) applied the barrier layer-forming composition 1 on the surface of the n-type ruthenium substrate (hereinafter also referred to as "n-type ruthenium substrate") after slicing. The printing width after drying at 150 ° C for 1 minute was observed using an optical microscope (manufactured by Olympus Co., Ltd., MX-51). The printing width is 180 μm, and the increase rate of 150 μm with respect to the set width of the mask is 120%. The results are shown in Table 1.

(Preparation of phosphorus diffusion liquid)

A 20% by mass aqueous solution of ammonium dihydrogen phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared, and a saturated aqueous solution of ammonium dihydrogen phosphate of the supernatant was used as a phosphorus diffusion liquid.

(thermal diffusion and etching steps)

The barrier layer forming composition 1 was applied to the surface of the n-type ruthenium substrate by using a mask pattern of a rectangular pattern of 20 mm × 45 mm, using a screen printing machine (MT-320T, manufactured by Microtek Technology Co., Ltd.) . After drying on a hot plate at 150 ° C for 5 minutes, it was dried by a hot plate at 500 ° C for 1 minute to form a barrier layer. Then, the phosphorus diffusion liquid was applied to the entire surface of the other substrate by a spin coater (manufactured by Mikasa Co., Ltd., MS-A100) at 500 rpm, and dried at 200 °C.

The surface of the two ruthenium substrates to which the barrier layer-forming composition 1 was applied and the surface on which the phosphorus diffusion liquid was applied were opposed to each other with a distance of 1 mm, and heated at 950 ° C for 10 minutes to diffuse phosphorus. To the tantalum substrate on which the barrier layer is formed. Then, the ruthenium substrate in which phosphorus is diffused and formed with a barrier layer is immersed in a 10% by mass aqueous HCl solution After 5 minutes, it was washed with water and further immersed in a 2.5% by mass aqueous HF solution for 5 minutes. After washing with water and drying to remove the barrier layer or the like, the following evaluation was performed.

(Measurement of sheet resistance)

The sheet resistance of the portion to which the barrier layer-forming composition 1 was applied was measured by a four-point probe method using a low resistivity meter (manufactured by Mitsubishi Chemical Corporation, Loresta-EP MCP-T360 type). The sheet resistance of the portion to which the barrier layer-forming composition 1 was applied was 220 Ω/□. The sheet resistance of the unapplied portion was 10 Ω/□.

Further, as a reference sample, the sliced n-type ruthenium substrate was immersed in a 2.5% by mass aqueous HF solution for 5 minutes, and the sheet resistance after washing and drying the mixture was measured. The sheet resistance is 240 Ω/□.

<Example 2>

(Preparation of composition 2 for barrier layer formation)

4 g of ethyl cellulose and 1 g of polyethylene glycol (number average molecular weight: 20,000) were added to 44 g of rosinol, dissolved at 160 ° C for 1 hour, and then allowed to cool to room temperature. Then, 20 g of calcium carbonate, 30 g of rosin alcohol, Disparlon 308 (manufactured by Nanben Chemical Co., Ltd., hydrogenated castor oil thixotropic agent), 1 g, and mixed in an agate mortar for 5 minutes to prepare a barrier layer-forming composition were added. 2. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 2 was used. The results are shown in Table 1.

<Example 3>

(Preparation of composition 3 for barrier layer formation)

In addition to the replacement of Disparlon 308 (made by Nanben Chemical Co., Ltd., A composition for forming a barrier layer was prepared in the same manner as in Example 2 except that 1 g of a hydrogenated castor oil-based thixotropic agent was used and 1 g of BYK-410 (manufactured by BYK Chemical Co., Ltd., urea urethane phthalamide) was used. Item 3. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 3 was used. The results are shown in Table 1.

<Example 4>

(Preparation of composition 4 for barrier layer formation)

4 g of ethyl cellulose, decylamine stearate (decomposition temperature: 320 ° C, melting point: 102 ° C to 104 ° C, manufactured by Wako Pure Chemical Industries, Ltd.) 7 g, Aerosil RY200 (Aerosil, Japan) The company manufactured, hydrophobically smoked cerium oxide, 0.5 g, was added to 38.5 g of rosin, and ethyl cellulose and decylamine stearate were dissolved at 160 ° C for 1 hour, and then allowed to cool to room temperature. Then, 20 g of calcium carbonate (manufactured by High Purity Chemical Research Co., Ltd., volume average particle diameter of 2.0 μm, amorphous particles) and 30 g of rosin alcohol were added, and mixed in an agate mortar for 5 minutes to prepare a barrier layer. Composition 4. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 4 was used. The results are shown in Table 1.

<Example 5>

(Preparation of composition 5 for barrier layer formation)

4 g of ethyl cellulose, 2 g of polyethylene glycol (quantitative molecular weight: 20,000), and 1 g of Aerosil RY200 (hydrophobic smoked cerium oxide) were added to 43 g of rosin and spent 1 hour at 160 ° C. Ethylcellulose and polyethylene glycol were dissolved and then allowed to cool to room temperature. Then, 20 g of calcium carbonate and 30 g of rosin were added, and the mixture was mixed in an agate mortar for 5 minutes to prepare a barrier layer-forming composition 5. In addition to using a barrier layer forming group Evaluation was performed in the same manner as in Example 1 except for the product 5. The results are shown in Table 1.

<Example 6>

(Preparation of composition for forming barrier layer 6)

4 g of ethyl cellulose and 2 g of polyethylene glycol (quantitative molecular weight: 20,000) were added to 44 g of butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.) at 160 ° C. It took 1 hour to dissolve, and then allowed to cool to room temperature. Then, 20 g of calcium carbonate and 30 g of butyl carbitol acetate were added, and they were mixed in an agate mortar for 5 minutes to prepare a barrier layer-forming composition 6. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 6 was used. The results are shown in Table 1.

<Example 7>

A barrier layer was formed in the same manner as in Example 1 except that 10 g of calcium carbonate and 10 g of zinc oxide (manufactured by High Purity Chemical Research Co., Ltd., average particle diameter: 1 μm) were used instead of 20 g of calcium carbonate. Composition 7. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 7 was used, and the results are shown in Table 2.

<Example 8>

(Preparation of composition 8 for barrier layer formation)

4 g of ethyl cellulose and 1 g of polyethylene glycol (number average molecular weight: 20,000) were added to 45 g of rosin, and the mixture was dissolved at 160 ° C for 1 hour, and then allowed to cool to room temperature. Then, calcium oxide (manufactured by Ube Materials Co., Ltd., super high-purity calcium oxide "CSQ", volume average particle diameter of 15 μm) 20 g, rosinol 30 g, and mixed in an agate mortar for 5 minutes to prepare a barrier layer The composition 8 for formation. except Evaluation was performed in the same manner as in Example 1 except that the barrier layer-forming composition 8 was used. The results are shown in Table 2.

<Example 9>

(Preparation of composition for forming barrier layer 9)

In addition to 20 g of calcium oxide, magnesium oxide (manufactured by Tateho Chemical Industries Co., Ltd., high-purity magnesium oxide "PUREMAG", volume average particle diameter of 0.5 μm) 20 g, in addition to the examples The barrier layer-forming composition 9 was prepared in the same manner. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 9 was used. The results are shown in Table 2.

<Example 10>

(Preparation of composition 10 for barrier layer formation)

A barrier layer was prepared in the same manner as in Example 1 except that polyethylene glycol (a number average molecular weight of 11,000, manufactured by Nippon Oil Co., Ltd.) was used instead of polyethylene glycol (the number average molecular weight was 20,000). The composition 10 for formation. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 10 was used. The results are shown in Table 2.

<Example 11>

(Preparation of composition for forming barrier layer 11)

0.5 g of ethyl cellulose, GEL ALL-D (manufactured by Shin Nippon Chemical Co., Ltd., oil gelling agent) was added to 45.5 g of rosin alcohol, and dissolved at 160 ° C for 1 hour to dissolve. Allow to cool to 100 °C. Then, calcium carbonate (manufactured by High Purity Chemical Research Institute Co., Ltd., volume average particle diameter of 2.0 μm, no 20 g of the shaped particles and 30 g of rosin were mixed in an agate mortar to prepare a composition 11 for forming a barrier layer. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 11 was used. The results are shown in Table 2.

<Example 12>

(Preparation of composition for forming barrier layer 12)

2 g of polyethylene glycol (quantitative molecular weight: 20,000), 1 g of ethyl cellulose, and S-LEC BM-1 (manufactured by Sekisui Chemical Co., Ltd., polyvinyl butyral resin) 4 g was added to 43 g of rosin, dissolved at 160 ° C for 1 hour, and then allowed to cool to room temperature. Then, 20 g of calcium carbonate (manufactured by High Purity Chemical Research Co., Ltd., volume average particle diameter of 2.0 μm, amorphous particles) and 30 g of rosin alcohol were added, and mixed in an agate mortar to prepare a barrier layer-forming composition. 12. Evaluation was performed in the same manner as in Example 1 except that the composition for forming the barrier layer 12 was used, and the results are shown in Table 2.

<Comparative Example 1>

(Preparation of composition for forming barrier layer C1)

4 g of ethyl cellulose was added to 46 g of rosin, dissolved at 160 ° C for 1 hour, and then allowed to cool to room temperature. Then, 20 g of calcium carbonate (manufactured by High Purity Chemical Research Co., Ltd., volume average particle diameter of 2.0 μm, amorphous particles) and 30 g of rosin alcohol were added, and mixed in an agate mortar to prepare a barrier layer-forming composition. C1. Evaluation was performed in the same manner as in Example 1 except that the composition for forming a barrier layer C1 was used. The results are shown in Table 1.

<Comparative Example 2>

(Preparation of composition for forming barrier layer C2)

4 g of ethyl cellulose, 4 g of S-LEC BM-1 (manufactured by Sekisui Chemical Co., Ltd., polyvinyl butyral resin) was added to 45 g of rosin, and dissolved at 160 ° C for 1 hour to dissolve. Let cool to room temperature. Then, 20 g of calcium carbonate (manufactured by High Purity Chemical Research Co., Ltd., volume average particle diameter of 2.0 μm, amorphous particles) and 30 g of rosin alcohol were added, and mixed in an agate mortar to prepare a barrier layer-forming composition. C2. Evaluation was performed in the same manner as in Example 1 except that the composition for forming a barrier layer C2 was used. The results are shown in Table 2.

<Comparative Example 3>

(Preparation of composition for forming barrier layer C3)

4 g of ethyl cellulose and 2 g of polyethylene glycol (number average molecular weight: 20,000) were added to 44 g of rosin, and the mixture was dissolved at 160 ° C for 1 hour, and then allowed to cool to room temperature. Then, 20 g of cerium oxide (manufactured by High Purity Chemical Research Co., Ltd., volume average particle diameter: 1.0 μm) and 30 g of rosin alcohol were added, and the mixture was mixed in an agate mortar for 5 minutes to prepare a barrier layer-forming composition C3. Evaluation was performed in the same manner as in Example 1 except that the barrier layer-forming composition C3 was used. The results are shown in Table 2.

As shown by the results of Tables 1 and 2, it is understood that the diffusion of the donor element or the acceptor element can be sufficiently prevented by using the composition for forming a barrier layer containing a specific metal compound, a dispersion medium, and a thixotropic agent. In addition, it is understood that by including the thixotropic agent, it is possible to suppress the enlargement of the line during printing or during drying when the fine line pattern is printed.

Japanese Patent Application No. 2012-002634, Japanese Patent Application No. 2012-037384, Japanese Patent Application No. 2012-037385, Japanese Patent Application No. 2012-037386, Japanese Patent Application No. 2012-107517, Japanese Patent Application The disclosures of the present application No. 2012-107518, the Japanese Patent Application No. 2012-237257, the Japanese Patent Application No. 2012-239146, and the Japanese Patent Application No. 2012-241267 are hereby incorporated by reference.

All of the documents, patent applications, and technical standards described in the specification are incorporated by reference to the same extent as the individual documents, patent applications, and technical specifications are incorporated by reference. Incorporated into this specification

10‧‧‧n type semiconductor substrate

11‧‧‧Block formation composition

12, 13‧‧‧Developing diffusion materials

12', 13'‧‧‧ Burning materials for coating diffusion materials

14‧‧‧n ⁺ type diffusion layer

15‧‧‧p ⁺ diffusion layer

16‧‧‧Anti-reflective film

17‧‧‧ Passivation film

18, 19‧‧‧ electrodes

Claims (24)

A composition for forming a barrier layer, comprising: a metal compound containing an alkaline earth metal or an alkali metal, a dispersion medium, and a thixotropic agent. The composition for forming a barrier layer according to claim 1, wherein the thixotropic agent comprises a compound selected from the group consisting of polyether compounds, fatty acid decylamines, organic fillers, inorganic fillers, hydrogenated castor oil, urea urethane oxime One or more of the group consisting of an amine, a polyvinylpyrrolidone, an anthrone-based thickening gelling agent, and an oil-based gelling agent. The composition for forming a barrier layer according to the first aspect of the invention, wherein the thixotropic agent comprises one or more selected from the group consisting of a polyether compound, a fatty acid guanamine, and an inorganic filler. The composition for forming a barrier layer according to any one of claims 1 to 3, wherein the thixotropic agent contains at least a polyether compound, and the polyether compound comprises the following formula (1) Expressed compound: In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group, n represents an integer of 1 or more, and R ² represents an exoethyl group or a propyl group. The composition for forming a barrier layer according to any one of claims 1 to 4, wherein the thixotropic agent contains at least a polyether compound, and the polyether compound has a number average molecular weight of 300 to 5,000,000. The composition for forming a barrier layer according to any one of claims 1 to 5, wherein the thixotropic agent contains at least a polyether compound, and the polyether compound has a number average molecular weight of 10,000 to 50,000. The barrier layer-forming composition according to any one of claims 1 to 6, wherein the thixotropic agent comprises at least a polyether compound, and the polyether compound comprises a polyethylene glycol, a poly One or more of the group consisting of propylene glycol and poly(ethylene glycol-propylene glycol) copolymer. The composition for forming a barrier layer according to any one of claims 1 to 7, wherein the thixotropic agent contains at least a fatty acid decylamine, and the fatty acid decylamine comprises the following general formula (2), a compound represented by the formula (3), the formula (4) or the formula (5): R ⁴ CONH ₂ (2) R ⁴ CONH-R ⁵ -NHCOR ⁴ ... (3) R ⁴ NHCO-R ⁵ -CONHR ⁴ (4) R ⁴ CONH-R ⁵ -NR ⁶ R ⁶ (5) Formula (2), Formula ( 3) In the formula (4) and the formula (5), R ⁴ and R ⁶ each independently represent an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and R ⁵ represents an alkylene group having 1 to 10 carbon atoms. The composition for forming a barrier layer according to any one of claims 1 to 8, wherein the thixotropic agent comprises at least a fatty acid decylamine, and the fatty acid decylamine comprises a guanamine containing stearic acid. One or more of the group consisting of N,N'-methylenebisstearate and dimethylaminopropyl decylamine stearate. The composition for forming a barrier layer according to any one of claims 1 to 9, wherein the thixotropic agent contains at least a fatty acid decylamine, and the fatty acid decylamine is evaded or decomposed at 400 ° C or lower. The barrier layer-forming composition according to any one of claims 1 to 10, wherein the thixotropic agent contains at least an inorganic filler, and the inorganic filler comprises smoked cerium oxide. The composition for forming an impurity diffusion layer according to claim 11, wherein the surface of the smoked cerium oxide is hydrophobized. The composition for forming a barrier layer according to any one of claims 1 to 12, further comprising an organic binder. The composition for forming a barrier layer according to claim 13, wherein the organic binder contains one or more selected from the group consisting of an acrylic resin, a cellulose resin, and a butyral resin. The barrier layer-forming composition according to any one of claims 1 to 14, wherein the alkaline earth metal or alkali metal-containing metal compound among all nonvolatile components of the barrier layer forming composition The total mass ratio is 0.5% by mass or more and less than 95% by mass. The barrier layer-forming composition according to any one of claims 1 to 15, wherein the alkaline earth metal or alkali metal-containing metal compound is selected from the group consisting of magnesium, calcium, sodium, potassium, lithium, and cesium. One or more of the groups consisting of 铯, 铍, 铍, 锶, 钡, and radium are used as the metal element. The barrier layer-forming composition according to any one of claims 1 to 16, wherein the alkaline earth metal or alkali metal-containing metal compound is selected from the group consisting of magnesium oxide, calcium oxide, potassium oxide, and magnesium carbonate. One or more of the group consisting of calcium carbonate, magnesium sulfate, calcium sulfate, calcium nitrate, magnesium hydroxide, and calcium hydroxide. The composition for forming a barrier layer according to any one of claims 1 to 17, wherein the dispersion medium comprises a solvent selected from the group consisting of water, an alcohol solvent, a glycol monoether solvent, and an isobornyl ring. One or more of the group consisting of an alcohol and a terpene solvent. The composition for forming a barrier layer according to any one of claims 1 to 18, which has a viscosity at 25 ° C of 0.5 Pa. s~400 Pa. s. The barrier layer forming composition according to any one of claims 1 to 19, wherein a barrier layer for partially suppressing a donor element or a barrier layer is formed on the semiconductor substrate. The diffusion of the acceptor element to the semiconductor substrate. A semiconductor substrate with a barrier layer, comprising a semiconductor substrate and a barrier layer, the barrier layer being formed from the barrier layer according to any one of claims 1 to 19, which is applied to the conductor substrate. Removing the above dispersion from the composition Obtained from at least a portion of the medium. A method for producing a substrate for a solar cell, comprising: applying a barrier layer forming composition according to any one of claims 1 to 19 on a semiconductor substrate to form a barrier layer And a step of diffusing the donor element or the acceptor element from the portion of the semiconductor substrate on which the barrier layer is not formed, and partially forming the impurity diffusion layer on the semiconductor substrate. The method for producing a substrate for a solar cell according to claim 22, wherein the method of applying the composition for forming a barrier layer is a printing method or an inkjet method. A method of producing a solar cell element, comprising the step of forming an electrode on an impurity diffusion layer of a substrate for a solar cell obtained by the production method according to claim 22 or claim 23.