JP2010067727A - Nano-ink precursor, nano-ink and film formed using nano-ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a precursor which can form a dense thin film useful for photovoltaics, an image sensor, or the like, easily by printing, and to provide ink containing the precursor, and a thin film. <P>SOLUTION: A nano-ink precursor includes an oxide produced by heat-treating a hydroxide having a composition A<SB>x</SB>(In<SB>1-y</SB>B<SB>y</SB>)(OH)<SB>m</SB>nH<SB>2</SB>O (where, 0.5≤x≤1.5, 0.1≤y≤0.9, m and n are optional digits, A is Cu and/or Zn, B is at least one of element selected from Ga, Fe, Al or Zn) wherein the BET specific surface area is 40-200 m<SP>2</SP>/g at 150-600°C. Nano-ink includes the nano-ink precursor, acrylic resin and a liquid organic compound of C3-C18, and a thin film is formed using the nano-ink. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a low-cost, safe and mass-produced precursor capable of easily forming a dense thin film useful for solar cells, image sensors and the like by printing, an ink containing the precursor, and The purpose is to provide a thin film.

  In recent years, technology for early practical application of new energy has been in the spotlight due to global environmental problems.

  New energy creation can be broadly divided into three categories: high-efficiency use of thermal power generation, power generation from gas energy sources that do not rely on solid or liquid energy sources, and power generation from natural energy sources such as wind and solar.

  For high-efficiency use of thermal power generation, in addition to conventional thermal power generation turbines, the combined use of gas turbines and fuel cells such as solid oxide / molten carbon dioxide will reduce power generation efficiency from 30% to 50%. It is a technique to raise.

  Further, hydrocarbons and hydrogen are attracting attention as gas energy sources, and application of fuel cells to stationary types and automobiles is expected.

  Unlike the above two methods, power generation from natural energy sources uses sunlight, wind power, wave power, geothermal heat, etc. In recent years, wind power generation and solar power generation are particularly popular in Europe. There is something to watch out for.

  Among solar power generation, there are various types of solar cells using the photovoltaic effect, such as silicon, compound semiconductor, and organic, and silicon currently occupies almost 90% of the market.

  In the silicon system, there is a separation method according to a form such as bulk or thin film, in addition to crystallinity such as single crystal, polycrystal, and amorphous. The conversion efficiency of bulk single crystal is good, but the cost in the manufacturing process is high, it can be produced at a lower cost, and the supply amount is tight. The shift is progressing.

  However, these silicon systems, which are undergoing a shift, have a conversion efficiency of 10 to 13%, which is lower than that of about 15% of a single crystal, and are inexpensive and excellent in quality from the consumer's perspective. Not.

On the other hand, a compound semiconductor CIS or CIGS solar cell that is expected to have a low conversion cost, a low CO ₂ generation amount during production, a theoretical conversion efficiency of tandem type, and a conversion efficiency as high as 25% or more as compared with silicon. Is being put to practical use.

  CIS or CIGS is a name given from the element symbol of copper (Cu) -indium (In) -gallium (Ga) -selenium (Se) / sulfur (S) which is mainly constituted.

  This CIS or CIGS manufacturing method is a technique using a lot of vacuum processes, that is, vapor deposition and sputtering, and it is an image that the semiconductor process is used as it is for the production of solar cells. Although such production facilities can be captured numerically as low production costs compared to silicon-based production, it is clearly over-investment when considering the production of solar cells that may be as low as five orders of magnitude compared to the semiconductor industry Can be judged.

Therefore, a method in which the process of making the CIS or CIGS a thin film having a thickness of several microns to several tens of microns is made a non-vacuum process has been studied. It is generally well known that CIGS is converted to CIGS by screen-printing the ink CIG and then circulating a gas such as H ₂ S or H ₂ Se.

  In order to obtain a CIS film or CIGS film whose conversion efficiency is superior to that of silicon, it is necessary to further improve the density and crystallinity of the CIG film or CIGS film with respect to ink.

  On the other hand, development of an image sensor using the photoelectric effect of CIGS is also underway.

  In conventional silicon-based image sensors, it is difficult to recognize an image with a brightness that is darker than the moonlight, and it is only possible to give a certain level of brightness to the object from the outside, or switch to a method using an expensive infrared camera There wasn't.

  Since the CIGS image sensor has a sensitivity of 6 to 10 times that of silicon, it is highly likely that it will be widely used in the future.

  In the case of dissemination, as with solar cells, there arises a problem of how to reduce the production cost, but non-vacuum process can be sufficient as this answer.

  In manufacturing a CIS thin film or a CIGS thin film, the following techniques have been proposed as existing techniques.

JP-A-2-180715 JP 7-89719 A JP-A-10-219472 Special table 2002-501003 gazette JP 2007-185664 A

  The techniques described in Patent Documents 1 to 5 are still not sufficient.

That is, in Patent Document 1 (Japanese Patent Laid-Open No. 2-180715), an alcohol solution containing copper chloride, indium chloride and selenious acid is dropped on a glass substrate to form a thin film, and then heated and fired to form CuInSe. Obtaining a thin film is described.
Patent Document 2 (Japanese Patent Application Laid-Open No. 7-89719) describes that copper powder, indium powder and sulfur powder are mixed and fired.
Patent Document 3 (Japanese Patent Laid-Open No. 10-219472) discloses that after applying to a substrate using a saturated monocarboxylic acid metal salt such as copper naphthenate and indium naphthenate, thermal decomposition is performed, and then selenium gas It is described that heat treatment is performed in an atmosphere.
Patent Document 4 (Japanese Patent Publication No. 2002-501003) describes forming metal chalcogenide nanoparticles by reacting a metal salt with a chalcogenide salt in an organic solvent.
Patent Document 5 (Japanese Patent Application Laid-Open No. 2007-185564) describes that a metal chalcogenide film is produced using a soluble hydrazine-based chalcogenite precursor.

  However, it is difficult to say that the techniques described in Patent Documents 1 to 5 can easily form a dense thin film.

  Accordingly, an object of the present invention is to provide a precursor capable of easily forming a dense thin film useful for solar cells, image sensors and the like by printing, an ink containing the precursor, and a thin film. .

  Any of the problems of production such as reduction in manufacturing cost and capital investment and chemical problems such as denseness and crystallinity of the CIG film when printed can be solved by the present invention described below.

That is, the present invention is a nano ink precursor comprising an oxide obtained by heat-treating a hydroxide having the following composition and a BET specific surface area of 40 to 200 m ² / g at 150 to 600 ° C. It is a body (Invention 1).
(Composition _{1) A x (In 1-} y B y) (OH) m nH 2 O
(0.5 ≦ x ≦ 1.5, 0.1 ≦ y ≦ 0.9. M and n are arbitrary numbers. A is Cu and / or Zn, and B is Ga, Fe. And at least one element selected from Al, Zn.)

Further, the present invention provides a hydroxide powder having the following composition 2 and a BET specific surface area of 40 to 200 m ² / g and a specific metal element C in a metal state (C is at least one selected from Se, S, Te, etc. It is a nano ink precursor made of an oxide obtained by heat-treating a mixture of at least one kind of element) at 150 to 600 ° C. (Invention 2).
(Composition _{2) A x (In 1-} y B y) (OH) m nH 2 O · C z
(0.5 ≦ x ≦ 1.5, 0.1 ≦ y ≦ 0.9. M and n are arbitrary numbers. A is Cu and / or Zn, and B is Ga, Fe. , Al, .z is at least one or more elements selected from Zn in molar ratio represented by _{(in 1-y B y)} / z, 1 / 1.9 to 1/6.)

  Further, the present invention is the nano ink precursor according to the present invention 1 or 2, wherein the Na amount is controlled to 1000 ppm to 8.0 wt% (Invention 3).

  Further, the present invention is a nano ink comprising the nano ink precursor according to the first or second aspect of the present invention, an acrylic resin, and two or more kinds of C3 to C18 liquid organic compounds containing a hydroxyl group (the fourth aspect of the present invention 4). ).

  Further, the present invention is a nano ink having a boiling point of 80 to 350 ° C. and a molecular weight of 60 to 280 g / mol (Invention 5).

  Further, the present invention is a nano ink in which the viscosity of the nano ink according to the present invention 4 or 5 is 0.1 to 10 Pa · sec at 30 ° C. (Invention 6).

Further, the present invention is a film coated with the nano ink according to any one of the present inventions 4 to 6, which has a film thickness of 0.5 to 50 μm and is subjected to heat treatment at 400 to 550 ° C. in a hydrogen stream. The membrane weight per ² is 0.2 to 20 mg / cm ² (Invention 7).

  The precursor according to the present invention can densely form a thin film useful as a solar cell or an image sensor by using an ink using the precursor.

  The nano ink according to the present invention can densely form a thin film useful as a solar cell or an image sensor.

  The film according to the present invention is a dense thin film with high crystallinity, and thus is useful as a thin film for solar cells with high conversion efficiency. In addition, it is useful as a thin film for an image sensor because the production cost can be reduced while maintaining the characteristics as a sensor.

  First, the nano ink precursor according to the present invention will be described.

The nano ink precursor according to the first aspect of the present invention is an oxide obtained by heat-treating a hydroxide having the composition 1 at 150 to 600 ° C.
(Composition _{1) A x (In 1-} y B y) (OH) m nH 2 O
Here, 0.5 ≦ x ≦ 1.5 and 0 ≦ y ≦ 0.9. m and n are arbitrary numbers. A is Cu and / or Zn, and B is at least one element selected from Ga, Fe, Al, and Zn.

  In the composition 1, when the composition x of the element A (Cu and / or Zn) is out of the above range, the characteristics as a solar cell or a sensor are extremely deteriorated. In addition, a single phase of chalcopyrite type crystal structure cannot be obtained. A more preferable range of x is 0.7 to 1.3.

  In composition 1, when the composition y of element B (at least one element selected from Ga, Fe, Al, Zn) exceeds 0.9, the forbidden band becomes too wide, so that the solar cell or sensor The characteristics of become worse. A more preferable range of y is 0 to 0.8.

The oxide particle powder constituting the nano ink precursor according to the first aspect of the invention has a BET specific surface area of 40 to 200 m ² / g as a raw material for obtaining the oxide particle powder. A more preferred hydroxide particle powder has a BET specific surface area of 50 to 180 m ² / g.

The BET specific surface area of the oxide particle powder constituting the nano ink precursor according to the present invention is preferably 15 to 120 m ² / g, more preferably 20 to 100 m ² / g.

The nano ink precursor according to the second aspect of the invention is an oxide particle powder having the composition 2.
(Composition _{2) A x (In 1-} y B y) (OH) m nH 2 O · C z
And 0.5 ≦ x ≦ 1.5 and 0 ≦ y ≦ 0.9. m and n are arbitrary numbers. A is Cu and / or Zn, B is at least one element selected from Ga, Fe, Al, and Zn, and C is at least one element selected from Se, S, and Te. And in a metallic state. z is in a molar ratio represented by _{(In 1-y B y)} / z, 1 / 1.9 to 1/6.

  In the composition 2, when the composition x of the element A (Cu and / or Zn) is out of the above range, the characteristics as a solar cell or a sensor are extremely deteriorated. In addition, a single phase of chalcopyrite type crystal structure cannot be obtained. A more preferable range of x is 0.7 to 1.3.

  In composition 2, when the composition y of element B (at least one element selected from Ga, Fe, Al, Zn) exceeds 0.9, the forbidden band becomes too wide, so that the solar cell or sensor The characteristics of become worse. A more preferable range of y is 0 to 0.8.

  In composition 2, when the composition z of element C (at least one element selected from Se, S, Te) is outside the above range, the volume fraction of chalcopyrite-type crystal structure particles is too low. The characteristics as a solar cell or sensor deteriorate. A more preferable range of z is 2-5.

  In composition 2, element C (at least one element selected from Se, S, Te) is in a metal state and exists in a state of zero valence. Oxides etc. are very toxic and are very difficult to handle. In addition, when a mixture of hydroxide, oxide, and metal is obtained by a liquid phase method, a C element compound (including a metal state, hereinafter the same) can be obtained at the same time, but a fine C element compound can be obtained. The raw material cost for obtaining the C element compound is not low, and it is forced to cope with the possibility of flowing out to the waste liquid at the time of filtration, resulting in a large capital investment.

The oxide particle powder constituting the nano ink precursor according to the second aspect of the present invention, and the BET specific surface area of the hydroxide particle powder used as a raw material for obtaining the oxide particles is 40 to 200 m ² / g.

  The average particle diameter of the oxide mixture particle powder constituting the nano ink precursor according to the present invention is preferably 5 to 50 nm.

  The particle shape of the oxide mixture particle powder constituting the nano ink precursor according to the present invention is not particularly limited, but a cubic shape, a rectangular parallelepiped shape, and a spherical shape are preferable.

  The nano ink precursor according to the present invention 1 or the present invention 2 is washed with water after production, but the amount of Na is controlled to 1000 ppm to 8.0 wt% by adjusting the degree of washing. If the amount of Na is less than 1000 ppm, the grain growth in the film is poor and a uniform film cannot be obtained. If it exceeds 8.0 wt%, the volume fraction of the chalcopyrite-type crystal structure particles becomes too low, so that the characteristics as a solar cell or a sensor are deteriorated. In addition, since a large amount of Na is present at the grain boundary, the contact between the particles is poor, and the transmission of heat, electrons, and the like is poor. Preferably, it is 1500 ppm to 6 wt%.

  Next, a method for producing a nano ink precursor will be described.

  The nano ink precursor according to the present invention can be obtained by neutralizing with an aqueous alkali solution using a metal salt having a desired composition, and drying and pulverizing the obtained precipitate after filtration and washing.

  What is necessary is just to add the addition rate of a metal salt so that it may become a desired composition rate.

  As alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, ammonia, urea aqueous solution, etc. are preferable.

  The addition ratio of the alkaline aqueous solution may be added so that the pH of the reaction solution is in the range of 3.5 to 9.0.

  When the nano ink precursor according to the present invention 2 contains C element (Se, S, Te), the metal concentration of the nano ink precursor obtained by the composition 1 is determined by thermal analysis, and the position of the C element derived therefrom is determined. It is obtained by adding a fixed amount to the precursor, and mixing and / or grinding by a dry method or a wet method.

When the nano ink precursor according to the present invention 2 contains C element (Se, S, Te), the molar equivalent z of the C element is a molar ratio represented by (In _1-y B _y ) / z. 1 / 1.9-1 / 6. Preferably it is 1/2 to 1 / 5.8, more preferably 1/2 to 1 / 5.5.

  Next, the nano ink according to the present invention will be described.

  The nano ink according to the present invention comprises the nano ink precursor of the present invention 1 or 2, the acrylic resin, and two or more kinds of liquid organic compounds of C3 to C18 containing a hydroxyl group.

  The acrylic resin is preferably used in a state dissolved in terpineol. In this state, the resin solid content is 30 to 40 wt%, the viscosity is 4 to 6 Pa · sec, the acid value is 20 to 30 mgKOH / g, and the molecular weight is PST. 300 to 400,000 is preferable in terms of conversion.

  As the liquid organic compound, at least two kinds of organic compounds having a hydroxyl group and having 3 to 18 carbon atoms may be used. For example, glycerin, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, tetraethylene glycol, isopropanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-octanol, 1-decanol, cis-9-octadecene-1 -Ol, cyclohexanol, methylcycline Hexanol, 2-ethylhexanol, hexanedioic acid, 2-isopropyl-5-methylcyclohexanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, phenol, terpineol, prenol, isovaleric acid, senecioic acid, Tiglic acid, 3-methyl-3-buten-2-ol, angelic acid, geraniol, nerol, farnesol, nerolidol, cineol, 1,2,4-butanetriol, polyvinyl alcohol, etc., of which at least terpineol It is preferable to use it.

  As the liquid organic compound, it is preferable to use a boiling point of 80 to 350 ° C. and a molecular weight of 60 to 280 g / mol. Furthermore, it is preferable that it is a liquid at 70 degreeC.

  The compounding amount of the nano ink according to the present invention is preferably such that the nano ink precursor is 20 to 40% by weight based on the whole ink, the acrylic resin is preferably 10 to 50% by weight, and the liquid organic compound is the whole ink. The amount is preferably 10 to 70% by weight.

  In addition, you may add various dispersing agents, a stabilizer, an emulsifier, and a pH adjuster to the nano ink which concerns on this invention as needed.

  The viscosity of the nano ink according to the present invention is preferably 0.1 to 10 Pa · sec. When the viscosity of the ink is out of the above range, it is difficult to print and apply. More preferably, it is 1 to 8 Pa · sec.

  Next, a method for producing a nano ink according to the present invention will be described.

  The nano ink which concerns on this invention should just mix and / or grind | pulverize a nano ink precursor, an acrylic resin, and 2 or more types of liquid organic compounds of C3-C18 containing a hydroxyl group by a conventional method.

  Mixing and / or grinding is not particularly limited. Examples include a Q-type mixer, a Henschel mixer, a Hoover Mahler, a (planet) ball mill, a rotation / revolution mixer, a high shear mixer, an apex mill, and a shaker.

  Next, the thin film according to the present invention will be described.

  In the thin film according to the present invention, the film thickness can be controlled to 0.5 to 50 μm. When the film thickness is less than 0.5 μm, it is difficult to have a sufficient function as a solar cell or a sensor. When it exceeds 50 μm, non-uniformity in film thickness exists, and it becomes difficult to produce another film on the thin film.

The thin film according to the present invention has a film weight of 0.2 to 20 mg / cm ² . When the film weight is 0.2 g / cm ² , it is difficult to have a sufficient function as a solar cell or a sensor. If it exceeds 20 g / cm ² , there will be non-uniformity in film thickness, making it difficult to produce another film on this thin film.

  Next, a method for manufacturing a thin film according to the present invention will be described.

  The thin film according to the present invention forms a coating film having a predetermined film thickness by spraying, coating, inkjet printing, screen printing, doctor blade printing, etc., using the nano ink, and then heat-treated in a reducing atmosphere. Can be obtained.

<Action>
The nano ink precursor according to the present invention is capable of forming a dense film by using an oxide via a hydroxide having the composition 1 or 2 described above.

  When the nano-ink precursor according to the present invention is used, the present inventor used a precursor composed of an oxide via a hydroxide having a large specific surface area as a reason why a dense film can be formed. It is presumed that the reaction proceeds easily.

  A typical embodiment of the present invention is as follows.

  The BET specific surface area value of the hydroxide mixture which is the precursor of the oxide mixture of the nano ink precursor is the B.sub. E. T.A. Measured by the method.

  The particle size of the nano ink precursor was measured using a transmission electron microscope (JEOL Ltd., JEM-1200EXII). The average value was obtained by selecting 120 particles for randomization and measuring the particle size.

  The composition analysis of the nano ink precursor sample was obtained by dissolving the sample with an acid and analyzing it using a plasma emission spectroscopic analyzer (Seiko Electronics Co., Ltd., SPS4000).

  The viscosity of the nano ink was measured at 30 ° C. using an E-type viscometer (Toki Sangyo Co., Ltd., TV-33 type viscometer).

  The thickness of the film produced with nano ink was measured by observing the vertical direction of the film with a scanning electron microscope (Hitachi High-Technologies Corporation, S-4800 FE-SEM (TYPE-I)).

Example 1 <Preparation of Nano Ink Precursor>
Cu (NO ₃ ) ₃ · 3H ₂ O (5.41 g), In (NO ₃ ) ₃ · 3H ₂ O (3.79 g) and Ga (NO ₃ ) ₃ · nH ₂ O (2.07 g) were dissolved in water to make 100 ml. . The mixed solution of Cu, In, and Ga was adjusted to pH 7.0 with 1N-NaOH at 25 ° C. to obtain a mixed hydroxide precipitate of light blue Cu, In, and Ga. The obtained hydroxide had a BET specific surface area of 71.7 m ² / g. The particle size of the precipitate was a 2-5 nm cube. After filtration and washing, it was vacuum-dried at 350 ° C., and a nanoink precursor oxide powder was obtained using a Taninaka grinder.
The BET specific surface area of the obtained powder was 40.2 m ² / g. The composition ratio of Cu / In / Ga was 1 / 0.6 / 0.4, which was the same as 1 / 0.6 / 0.4 of the charged composition. As a precaution, the amounts of Cu, In, and Ga in the filtrate were analyzed, and all were 0 mg / L. The amount of Na contained was 3.0 wt%.

<Preparation of nano ink>
0.3 g of the nano ink precursor as a powder, 0.8 g of DA-50 (manufactured by Toagosei Co., Ltd.) in which acrylic resin is dissolved in terpineol (acrylic resin component is about 34% by weight), 1-octanol (reagent manufactured by Mitsuwa Chemical) ) 1.0 g was weighed into a 25 ml plastic container. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 2.2 Pa · sec at 30 ° C.

<Film formation from nano ink>
Blue glass having a 1.5 cm square and a thickness of 200 μm was set in an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.). 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.25 mm / sec using a variable applicator. This was dried with a dryer at 100 ° C. for 10 minutes. Subsequently, the reaction vessel was sealed in a 25 mmφ SUS reaction can and purged with Ar gas. Subsequently, the temperature was raised to 500 ° C. at 10 ° C./min while flowing Ar gas. During this time, after the reactor internal temperature reached 150 ° C., the Ar gas was stopped and the temperature was raised to hydrogen gas. Aging was performed at 500 ° C. for 1 h, and the hydrogen gas was stopped and quenched while purging with an Ar gas. The film on the glass was not cracked or peeled off, and its thickness was 3 μm. The film weight per cm ² was 0.23 mg / cm ² .

Example 2
_{Cu (NO 3) 3 · 3H} 2 O 5.41g and _{In (NO 3) 2 · 3H} 2 O 3.79g, Ga (NO 3) 3 · nH 2 O 1.55g, Fe (NO 3) 3 · 9H and ₂ O 0.72 g was 100ml dissolved in water. At 35 ° C., the pH was adjusted to 7.2 using 1N-NaOH to obtain an almost light blue mixed hydroxide precipitate of Cu, In, Ga, and Fe. The BET specific surface area of the obtained hydroxide was 80.4 m ² / g. The particle size of the precipitates was a 2-5 nm cubic shape and an 8 nm × 200 nm needle-like mixture. After filtration and washing, it was vacuum-dried at 350 ° C., and a nanoink precursor oxide powder was obtained using a Taninaka grinder.
The obtained powder had a BET specific surface area of 55.2 m ² / g. The composition ratio of Cu / In / Ga / Fe was 1 / 0.6 / 0.3 / 0.1, which was the same as 1 / 0.6 / 0.3 / 0.1 of the charged composition. As a precaution, the amounts of Cu, In, Ga, and Fe in the filtrate were analyzed, but Cu was detected at 0.12 mg / L, but the others were not detected. The amount of Na contained was 5.2 wt%.

  0.4 g of the nano ink precursor as a powder, 1.6 g of DA-50 (manufactured by Toagosei) in which acrylic resin is dissolved in terpineol, and 1.5 g of 1-octanol (Mitsuwa Chemical reagent) in a 25 ml plastic container Weighed. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 1.5 Pa · sec at 30 ° C.

A blue glass obtained by sputtering and depositing 1.5 cm square and 1.4 mm thick Mo with a thickness of 1 μm was set on an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.) with the Mo film facing up. 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.25 mm / sec using a variable applicator. It was dried for 10 minutes with a dryer at 100 ° C. This was heat-treated in the same manner as in Example 1 above. The obtained film was not cracked or peeled off, and its thickness was 1.5 μm. The film weight per cm ² was 0.38 mg / cm ² .

Example 3
In the same manner as in Example 1, Cu, In and Ga light blue mixed hydroxide precipitates were obtained. After filtration and washing, it was vacuum dried at 150 ° C. and pulverized using a Taninaka pulverizer. This was again heat-treated at 350 ° C. to obtain an oxide powder.
The BET specific surface area of the obtained powder was 38.3 m ² / g. The composition ratio of Cu / In / Ga was 1 / 0.6 / 0.4, which was the same as 1 / 0.6 / 0.4 of the charged composition. As a precaution, the amounts of Cu, In, and Ga in the filtrate were analyzed, and all were 0 mg / L. Subsequently, 0.12 g of Se metal of 400 mesh or less was added to 0.20 g of the nanoink precursor powder, and mixed and pulverized in a mortar to obtain a nanoink precursor. Based on the composition _{2 (In 1-y B y} ) / z ( molar ratio) was 1 / 2.0. The amount of Na contained was 3.2 wt%.

  0.26 g of the nano ink precursor as a powder, 0.3 g of DA-50 (manufactured by Toagosei Co., Ltd.) in which an acrylic resin is dissolved in terpineol, 1.0 g of 1-octanol (manufactured by Mitsuwa Chemical), oleylamine (reagent manufactured by Aldrich) ) 0.003 ml was weighed into a 25 ml plastic container. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 5.2 Pa · sec at 30 ° C.

Blue glass having a 1.5 cm square and a thickness of 200 μm was set in an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.). 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.25 mm / sec using a variable applicator. It was dried for 10 minutes with a dryer at 100 ° C. This was heat-treated as in Example 1 above. The obtained film was not cracked or peeled off, and its thickness was 1.5 μm. The film weight per cm ² was 0.30 mg / cm ² .

Example 4
Similar to Example 2, a substantially cyan mixed hydroxide precipitate of Cu, In, Ga, and Fe was obtained. After filtration and washing, it was vacuum dried at 150 ° C. and pulverized using a Taninaka pulverizer. This was again heat-treated at 250 ° C. to obtain an oxide powder.
The BET specific surface area of the obtained powder was 60.3 m ² / g. The composition ratio of Cu / In / Ga / Fe was 1 / 0.6 / 0.3 / 0.1, which was the same as 1 / 0.6 / 0.3 / 0.1 of the charged composition. As a precaution, the amounts of Cu, In, Ga, and Fe in the filtrate were analyzed, but Cu was detected at 0.12 mg / L, but the others were not detected. Subsequently, 0.19 g of Se metal of 400 mesh or less was added to 0.20 g of the nanoink precursor powder, and mixed and pulverized in a mortar to obtain a nanoink precursor. Based on the composition _{2 (In 1-y B y} ) / z ( molar ratio) was 1 / 3.8. The amount of Na contained was 5.2 wt%.

  0.3 g of the nano ink precursor as a powder, 1.2 g of DA-50 (manufactured by Toagosei Co., Ltd.) in which an acrylic resin is dissolved in terpineol, 1.0 g of 1-octanol (manufactured by Mitsuwa Chemical), oleylamine (reagent manufactured by Aldrich) ) 0.002 g was weighed into a 25 ml plastic container. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 4.2 Pa · sec at 30 ° C.

A blue glass obtained by chemically depositing 1.5 cm square and 1.4 mm thick Mo with a thickness of 1 μm was set on an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.) with the Mo film facing up. 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.25 mm / sec using a variable applicator. It was dried for 10 minutes with a dryer at 100 ° C. This was heat-treated as in Example 1 above. The obtained film was not cracked or peeled off, and its thickness was 3.2 μm. The film weight per cm ² was 0.85 mg / cm ² .

Example 5
Cu (NO ₃ ) ₂ .3H ₂ O 5.41 g, In (NO ₃ ) ₃ .3H ₂ O 1.90 g, Ga (NO ₃ ) ₃ .nH ₂ O 3.10 g, Al (NO ₃ ) ₃ .6H into an aqueous solution of 100ml by dissolving the ₂ O 0.67 g. At 50 ° C., the pH was adjusted to 6.8 with 1N NaOH to obtain a green mixed hydroxide precipitate of Cu, In, Ga, and Al. The obtained hydroxide had a BET specific surface area of 89.5 m ² / g. The particle size of the precipitate was a 3-6 nm cubic shape and a 10 nm × 200 nm needle-like mixture. After filtration and washing, it was vacuum dried at 150 ° C. and pulverized using a Taninaka pulverizer. This was again heat-treated at 350 ° C. to obtain an oxide powder.
The obtained powder had a BET specific surface area of 64.0 m ² / g. The composition ratio of Cu / In / Ga / Al was 1 / 0.3 / 0.6 / 0.1, which was the same as the charged composition 1 / 0.3 / 0.6 / 0.1. As a precaution, the amounts of Cu, In, Ga, and Al in the filtrate were analyzed, but Cu was detected at 0.08 mg / L, but the others were not detected.
Subsequently, 0.23 g of Se metal of 400 mesh or less was added to 0.20 g of the nanoink precursor powder, and the nanoink precursor was obtained by mixing and grinding in a mortar. Based on the composition _{2 (In 1-y B y} ) / z ( molar ratio) was 1 / 3.8. The amount of Na contained was 2550 ppm.

  0.5 g of the nano ink precursor as a powder, 2.0 g of DA-50 (manufactured by Toagosei Co., Ltd.) in which an acrylic resin is dissolved in terpineol, 0.5 g of 1-decanol (manufactured by Mitsuwa Chemical), ethylene glycol (manufactured by Aldrich) Reagent) 0.25 g and Poval PVA-205S (polyvinyl alcohol, Kuraray) 0.08 g were weighed in a 25 ml plastic container. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 3.2 Pa · sec at 30 ° C.

A blue glass obtained by chemically depositing 1.5 cm square W and 1.4 mm thick W with a thickness of 1 μm was set on an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.) with the W film facing up. 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.25 mm / sec using a variable applicator. It was dried for 10 minutes with a dryer at 100 ° C. This was heat-treated as in Example 1 above. The obtained film was not cracked or peeled off, and its thickness was 1.0 μm. The film weight per cm ² was 0.92 mg / cm ² .

Example 6
A solution of 5.41 g of Cu (NO ₃ ) ₂ .3H ₂ O, 5.06 g of In (NO ₃ ) ₃ .3H ₂ O and 1.03 g of Ga (NO ₃ ) ₃ .nH ₂ O was dissolved in 100 ml of an aqueous solution. did. The pH was adjusted to 7.0 using 1 N NaOH at 35 ° C., and a light-colored mixed hydroxide precipitate of Cu, In, and Ga was obtained. The BET specific surface area of the obtained hydroxide was 82.3 m ² / g. The particle size of the precipitate was a 2-5 nm cube. After filtration and washing, it was vacuum dried at 150 ° C. and pulverized using a Taninaka pulverizer. This was again heat-treated at 550 ° C. to obtain an oxide powder.
The BET specific surface area of the obtained powder was 41.1 m ² / g. The composition ratio of Cu / In / Ga was 1 / 0.8 / 0.2, which was the same as 1 / 0.8 / 0.2 of the charged composition. As a precaution, the amounts of Cu, In, and Ga in the filtrate were analyzed, and all were 0 mg / L.
Subsequently, 1.2 g of the nano ink precursor powder is put in a crucible and heat-treated at 480 ° C. for 1.5 h under a flow of H ₂ Se gas and H ₂ S gas at a Se / S = 0.82 / 0.18 molar ratio. Thus, a nano ink precursor was obtained. Based on the composition _{2 (In 1-y B y} ) / z ( molar ratio) was 1 / 2.1. The amount of Na contained was 3.8 wt%.

0.5 g of the nano ink precursor as a powder, 2.0 g of DA-50 (manufactured by Toagosei Co., Ltd.) in which an acrylic resin is dissolved in terpineol, 0.5 g of 1-decanol (manufactured by Mitsuwa Chemical), 1-cyclohexanol ( Aldrich reagent (0.12 g) was weighed into a 25 ml plastic container. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 2.8 Pa · sec at 30 ° C.
1.0 g of the nano ink precursor as a powder, 1.6 g of DA-50 (manufactured by Toagosei) in which an acrylic resin is dissolved in terpineol, 1.0 g of 1-octanol (manufactured by Mitsuwa Chemical), ethylene glycol monobutyl ether ( Aldrich reagent (0.2 g) was weighed into a 25 ml plastic container. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 1.3 Pa · sec at 30 ° C.

Blue glass obtained by chemically vapor-depositing 1.5 cm square and 1.4 mm thick Ag with a thickness of 1 μm was set on an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.) with the Ag film facing up. 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.45 mm / sec using a variable applicator. It was dried for 10 minutes with a dryer at 100 ° C. This was heat-treated as in Example 1 above. Subsequently, the reaction vessel was sealed in a 25 mmφ SUS reaction can and purged with Ar gas. Subsequently, the temperature was raised to 520 ° C. at 10 ° C./min while flowing Ar gas. During this time, after the reactor internal temperature reached 150 ° C., the Ar gas was stopped and the temperature was raised to hydrogen gas. Aging was carried out at 520 ° C. for 3 hours, the hydrogen gas was stopped, and the glass was rapidly cooled while being purged with Ar gas, and the glass coated with the nano ink was taken out at room temperature. The obtained film was not cracked or peeled off, and its thickness was 1.5 μm. The film weight per cm ² was 0.49 mg / cm ² .

Example 7
Cu (NO ₃ ) ₂ .3H ₂ O 5.41 g, In (NO ₃ ) ₃ .3H ₂ O 3.16 g, Ga (NO ₃ ) ₃ .nH ₂ O 1.03 g, Zn (NO ₃ ) ₃ .6H 1.92 g of ₂ O was dissolved to make a 100 ml aqueous solution. The mixture was adjusted to pH 6.8 using 1N NaOH at 50 ° C. to obtain a green mixed hydroxide precipitate of Cu, In, Ga and Zn. The obtained hydroxide had a BET specific surface area of 110 m ² / g. The particle size of the precipitate was a 3-7 nm cubic shape and a 10 nm × 200 nm needle-like mixture. After filtration and washing, it was vacuum dried at 150 ° C. and pulverized using a Taninaka pulverizer. This was again heat-treated at 350 ° C. to obtain an oxide powder.
The BET specific surface area of the obtained powder was 83.2 m ² / g. The composition ratio of Cu / In / Ga / Zn was 1 / 0.5 / 0.2 / 0.3, which was the same as 1 / 0.5 / 0.2 / 0.3 of the charged composition. As a precaution, the amounts of Cu, In, Fe, and Zn in the filtrate were analyzed, but Cu was detected at 0.12 mg / L, but the others were not detected.
Subsequently, 1.2 g of the nano ink precursor powder was put into a crucible and heat treated at 485 ° C. for 1 h under the flow of Se / S = 0.82 / 0.18 molar ratio of H ₂ Se gas and H ₂ S gas. A nano ink precursor was obtained. Based on the composition _{2 (In 1-y B y} ) / z ( molar ratio) was 1 / 2.8. The amount of Na contained was 1.2 wt%.

  0.5 g of the nano ink precursor as a powder, 2.0 g of DA-50 (manufactured by Toagosei) in which an acrylic resin is dissolved in terpineol, 0.8 g of 1-octanol (manufactured by Mitsuwa Chemical), ethylene glycol monobutyl ether ( Aldrich reagent (0.2 g) was weighed into a 25 ml plastic container. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 2.3 Pa · sec at 30 ° C.

Blue glass having a 1.5 cm square and a thickness of 200 μm was set in an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.). 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.42 mm / sec using a variable applicator. It was made to dry for 10 minutes with a 50 degreeC vacuum dryer. This was heat-treated as in Example 6 above. The obtained film was not cracked or peeled off, and its thickness was 1.6 μm. The film weight per cm ² was 0.51 mg / cm ² .

Example 8
5.41 g of Cu (NO ₃ ) ₂ .3H ₂ O and 3.79 g of In (NO ₃ ) ₃ .3H ₂ O, 1.34 g of Al (NO ₃ ) ₃ .9H ₂ O, Zn (NO ₃ ) ₃ .6H 1.28 g of ₂ O was dissolved to make a 100 ml aqueous solution. The pH was adjusted to 6.8 using 1N NaOH at 50 ° C. to obtain a green mixed hydroxide precipitate of Cu, In, Al, and Zn. The obtained hydroxide had a BET specific surface area of 150.2 m ² / g. The particle size of the precipitate was a 3-7 nm cubic shape and a 9 nm × 200 nm needle-like mixture. After filtration and washing, it was vacuum dried at 150 ° C. and pulverized using a Taninaka pulverizer. This was again heat-treated at 550 ° C. to obtain an oxide powder.
The BET specific surface area of the obtained powder was 91.0 m ² / g. The composition ratio of Cu / In / Al / Zn was 1 / 0.6 / 0.2 / 0.2, which was the same as 1 / 0.6 / 0.2 / 0.2 of the charged composition. As a precaution, the amounts of Cu, In, Al, and Zn in the filtrate were analyzed, but Cu was detected at 0.15 mg / L, but the others were not detected.
Subsequently, 0.46 g of Se metal of 400 mesh or less was added to 0.20 g of the nanoink precursor powder, and the nanoink precursor was obtained by mixing and grinding in a mortar. Based on the composition _{2 (In 1-y B y} ) / z ( molar ratio) was 1 / 5.8. The amount of Na contained was 5.3 wt%.

  0.5 g of the nano ink precursor as a powder, 4.0 g of DA-50 (manufactured by Toagosei Co., Ltd.) in which acrylic resin is dissolved in terpineol, and 0.8 g of 1-octanol (Mitsuwa Chemical reagent) in a 25 ml plastic container Weighed. To this was added 10 g of 1.5 mmφ zirconia beads, and the nano ink was prepared by shaking and mixing well. The viscosity of the nano ink was 6.3 Pa · sec at 30 ° C.

It was set in an automatic coating apparatus (PI-1210 manufactured by Tester Sangyo Co., Ltd.) with the surface where Mo was chemically vapor-deposited with a thickness of 1 μm on a 1.5 cm square blue glass having a thickness of 1.4 mm. 1.5 mL of nano ink was dropped on glass and stretched at a speed of 0.25 mm / sec using a variable applicator. It was made to dry for 10 minutes with a 50 degreeC vacuum dryer. This was heat-treated as in Example 6 above. The obtained film was not cracked or peeled off, and its thickness was 30.0 μm. The film weight per cm ² was 15.0 mg / cm ² .

Comparative Example 1
In the same manner as in Example 4, a mixed hydroxide of light blue Cu, In, Ga and Al was obtained. This was heat-treated at 400 ° C. in the air and pulverized with a Taninaka pulverizer to obtain a dry powder close to black. It was confirmed by analysis with an X-ray diffractometer that Cu, In, Ga, and Al are in an oxide state.
The BET specific surface area of the obtained powder was 121.0 m ² / g. The composition ratio of Cu / In / Ga / Al was 1 / 0.5 / 0.3 / 0.2, which was the same as 1 / 0.5 / 0.3 / 0.2 of the charged composition. Subsequently, 2.0 g of Se metal of 400 mesh or less was added to 0.8 g of the nanoink precursor powder, and mixed and pulverized in a mortar to obtain a nanoink precursor. Based on the composition _{2 (In 1-y B y} ) / z ( molar ratio) was 1 / 3.3. The amount of Na contained was 8.3 wt%.

  1.5 g of the nano ink precursor as a powder, 1.0 g of DA-50 (manufactured by Toagosei) in which acrylic resin is dissolved in terpineol, and 1.5 g of 1-decanol (manufactured by Mitsuwa Chemical) in a 25 ml plastic container. Weighed. To this, 10 g of 1.5 mmφ zirconia beads was added and shaken and mixed well. However, it gelled and did not become ink.

Comparative Example 2
In the same manner as in Example 1, a mixed hydroxide of light blue Cu, In and Ga was obtained. This was dried at 80 ° C. and pulverized with a Taninaka pulverizer.
The BET specific surface area of the obtained powder was 101.2 m ² / g. The In / Ga composition ratio was 1 / 0.6 / 0.4, which was the same as 1 / 0.6 / 0.4 of the charged composition. The amount of Na contained was 200 ppm.

  0.8 g of the nano ink precursor as a powder, 1.0 g of DA-50 (manufactured by Toagosei Co., Ltd.) in which acrylic resin is dissolved in terpineol, and 1.3 g of ethanol (manufactured by Mitsuwa Chemical) are weighed in a 25 ml plastic container. It was. To this, 10 g of 1.5 mmφ zirconia beads was added and shaken and mixed well. However, it gelled and did not become ink.

  INDUSTRIAL APPLICABILITY The present invention is very useful because it can industrially print a manufacturing process of a solar cell, a sensor, a semiconductor, and the like, and can greatly reduce the capital investment.

Claims (7)

A nano-ink precursor comprising an oxide obtained by heat-treating a hydroxide having the following composition and a BET specific surface area of 40 to 200 m ² / g at 150 to 600 ° C.
(Composition _{1) A x (In 1-} y B y) (OH) m nH 2 O
(0.5 ≦ x ≦ 1.5, 0.1 ≦ y ≦ 0.9. M and n are arbitrary numbers. A is Cu and / or Zn, and B is Ga, Fe. And at least one element selected from Al, Zn.) A hydroxide powder having the following composition 2 and a BET specific surface area of 40 to 200 m ² / g and a specific metal element C in a metallic state (C is at least one element selected from Se, S, Te, etc.) A nano-ink precursor comprising an oxide obtained by heat-treating the mixture at 150 to 600 ° C.
(Composition _{2) A x (In 1-} y B y) (OH) m nH 2 O · C z
(0.5 ≦ x ≦ 1.5, 0.1 ≦ y ≦ 0.9. M and n are arbitrary numbers. A is Cu and / or Zn, and B is Ga, Fe. , Al, .z is at least one or more elements selected from Zn in molar ratio represented by _{(in 1-y B y)} / z, 1 / 1.9 to 1/6.)   The nano ink precursor according to claim 1 or 2, wherein the amount of Na is controlled to 1000 ppm to 8.0 wt%.   A nano ink comprising the nano ink precursor according to claim 1 or 2, an acrylic resin, and two or more kinds of C3 to C18 liquid organic compounds containing a hydroxyl group.   The liquid organic compound according to claim 4, wherein the liquid organic compound has a boiling point of 80 to 350 ° C and a molecular weight of 60 to 280 g / mol.   The nano ink according to claim 4, wherein the nano ink has a viscosity of 0.1 to 10 Pa · sec at 30 ° C. It is a film | membrane which apply | coated the nano ink in any one of Claim 4 thru | or 6, Comprising: Film thickness is 0.5-50 micrometers, and the film | membrane weight per cm < ² > after heat-processing at 400-550 degreeC in hydrogen stream is the film weight. A membrane, which is 0.2 to 20 mg / cm ² .