JP5018552B2 - ZnO vapor deposition material, method for producing the same, and ZnO film formed thereby - Google Patents

Description

The present invention relates to a transparent conductive film used for, for example, a solar cell, a liquid crystal display device, an electroluminescence display device, a transparent electrode of a transparent piezoelectric sensor of a touch panel device, an active matrix driving device constituting the display device, and an antistatic conductive film coatings, gas sensors, electromagnetic shielding panels, piezoelectric devices, photoelectric conversion devices, light-emitting device, formed thereby ZnO deposition material and a manufacturing method thereof as well as used for forming the film used like a thin film type secondary battery The present invention relates to a ZnO film.

  In recent years, a transparent conductive film is indispensable when manufacturing photoelectric conversion devices such as solar cells. An ITO film (indium oxide film doped with tin) is known as a conventional transparent conductive film. The ITO film has the advantages of excellent transparency and low resistance.

  On the other hand, cost reduction is required for solar cells, liquid crystal display devices, and the like. However, since indium is expensive, when an ITO film is used as a transparent conductive film, the solar cell inevitably becomes expensive. In addition, when manufacturing solar cells or the like, amorphous silicon is deposited on the transparent conductive film by plasma CVD. At that time, if the transparent conductive film is an ITO film, There was also a problem that the ITO film deteriorated by the hydrogen plasma.

In order to eliminate these points, it has been proposed to use a zinc oxide-based film doped with a conductive active element such as Al, B, and Si that can be produced at a lower cost as a transparent conductive film such as a solar cell, A zinc oxide-based sputtering target for forming this zinc oxide-based film by sputtering has been proposed (for example, see Patent Document 1). According to this zinc oxide-based sputtering target, an extremely low resistance zinc oxide-based sintered body can be obtained by containing a predetermined amount of the conductive active element with respect to zinc. It is said that the higher the dispersibility, the higher the sintered density and the higher the conductivity.
JP-A-6-2130 (Claims 2, 3 and 4 of Claims)

However, if sputtering is performed while applying a high voltage to form a high-speed film using the conventional zinc oxide sputtering target, abnormal discharge is likely to occur, the discharge state is unstable, and the target is consumed unevenly. However, there was a problem that it was difficult to obtain a low-resistance film due to composition deviation in the obtained film. On the other hand, when the input power is reduced and the voltage is lowered, the film formation rate is reduced, and the film formation efficiency of the zinc oxide film is greatly reduced.
An object of the present invention is to provide a ZnO vapor deposition material capable of forming a film having a high conductivity approaching that of an ITO film at a high speed, a manufacturing method thereof, and a ZnO film using the same.

The invention according to claim 1 is a ZnO vapor deposition material used for forming a transparent conductive film.
The characteristic structure consists of a pellet mainly composed of ZnO, the pellet contains both elements of Ce and B, Ce is higher in content than B, and the content of Ce is 3 to 14.9% by mass. , B is in a range of 1 to 10% by mass.
In the invention according to claim 1, since two elements of Ce and B are contained in the above-described content ratio in the pellet mainly composed of ZnO, when this ZnO vapor deposition material is used, the ZnO film having high conductivity approaching that of the ITO film. Can be formed.

The invention according to claim 2 is the ZnO vapor deposition material according to claim 1, wherein the total content ratio of Ce and B is in the range of 4 to 15% by mass.
In the invention according to claim 2, by the total content ratio of Ce and B in ZnO deposition material is in the range of 4-15 wt%, excellent effect in conductive properties and spectral characteristics.

The invention according to claim 3 is the invention according to claim 1, wherein the ZnO pellet is a polycrystalline or single crystal ZnO vapor deposition material.
In the invention according to claim 3, when the ZnO pellet is polycrystalline because the effect changes notably depending on the composition but not the difference in the structure of whether the ZnO pellet is polycrystalline or single crystal. In addition, if a ZnO film is formed using the ZnO vapor deposition material as long as it has a composition within the range described in claim 1 even if it is a single crystal, the ZnO film has a high conductivity approaching that of the ITO film. Sex is obtained.
The invention according to claim 4 is a method for producing the ZnO vapor deposition material according to any one of claims 1 to 3, wherein the content ratio of Ce in the ZnO powder and the ZnO vapor deposition material is 3 to 14.9 mass. % Concentration of CeO ₂ powder, B ₂ O ₃ powder in which the content ratio of B in the ZnO vapor deposition material is in the range of 1 to 10% by mass , a binder, and an organic solvent are mixed to give a concentration of 30 to A slurry of 75 mass% with a Ce content in the ZnO vapor deposition material higher than the content of B is prepared, and the slurry is spray-dried to produce a mixed granulated powder having an average particle size of 50 to 250 μm. Then, the mixed granulated powder is put into a predetermined mold and molded at a predetermined pressure, and a molded body obtained by molding is sintered at a temperature of 1000 ° C. or more for 1 to 10 hours to obtain a polycrystalline ZnO vapor deposition material comprising pellets It is the manufacturing method of the ZnO vapor deposition material characterized by obtaining.

The invention according to claim 5 is formed by a vacuum film forming method using the ZnO vapor deposition material according to any one of claims 1 to 3 or the ZnO vapor deposition material obtained by the manufacturing method according to claim 4 as a target material. ZnO film.
In the invention according to claim 5 , a ZnO film is formed using the ZnO vapor deposition material according to any one of claims 1 to 3 or the ZnO vapor deposition material obtained by the manufacturing method according to claim 5. Therefore, this ZnO film can have high conductivity approaching that of the ITO film.

The invention according to claim 6 is the invention according to claim 5 , wherein the vacuum film formation method is a ZnO film which is an electron beam evaporation method, an ion plating method, a sputtering method or a plasma evaporation method.

As described above, according to the ZnO vapor deposition material used to form the transparent conductive film of the present invention, the ZnO vapor deposition material is composed of pellets mainly composed of ZnO, and the pellets contain both elements of Ce and B. Is higher than B, the Ce content is 3 to 14.9% by mass, and the B content is in the range of 1 to 10% by mass. A ZnO film having high electrical conductivity can be formed. Since the ZnO vapor deposition material of the present invention contains both Ce and B as additive elements, a crystal distorted by Ce having an ionic radius larger than Zn is recovered and matched by adding B having a small ionic radius, thereby increasing the transmittance. A high-durability ZnO film can be formed, and a highly durable ZnO film can be formed by obtaining a film with excellent denseness.
Further, since the ZnO film according to the present invention is formed using the ZnO vapor deposition material according to the present invention or the ZnO vapor deposition material obtained by the production method of the present invention , high conductivity and high transmittance can be obtained. Furthermore, the durability of the membrane is improved.

Next, the best mode for carrying out the present invention will be described.
The present inventor has investigated in detail the effect of conductivity on the ZnO vapor deposition material and the additive species in the ZnO film formed using this vapor deposition material and its content. As an additive element in the ZnO pellet, It was confirmed that the content ratios of the two elements, Ce and B, were greatly affected. In the ZnO pellet, the conductivity generally becomes better as the content ratio of the two elements Ce and B increases. However, when the content is further increased, the conductivity deteriorates. It has been found that there is an optimum content range for the elements.

The ZnO vapor deposition material according to the present invention contains ZnO as a main component and contains both elements of Ce and B. The use of B having a small ionic radius can improve the film consistency. Since two types of elements, Ce and B, are included as additive elements, a ZnO film having high conductivity can be formed by expressing and maintaining a large amount of overelectrons that contribute to conduction. Ce in the ZnO vapor deposition material according to the present invention is in the range of 3 to 14.9% by mass. This is because when Ce is 3 % by mass which is the lower limit, the conductivity is remarkably lowered, and when it exceeds 14.9% by mass which is the upper limit, the transmittance is remarkably lowered. B is in the range of 1 to 10% by mass. This is because when B is less than the lower limit of 1 % by mass, the conductivity is remarkably lowered, and when it exceeds 10% by mass of the upper limit, composition deviation occurs during vapor deposition. Among these, the Ce element is preferably in the range of 3 to 6% by mass, and B is preferably in the range of 1 to 3% by mass. In order to maintain a dense crystal structure, the Ce content is set higher than the B content. On the other hand, when the Ce content ratio is higher than the B content ratio, conductivity and transmittance deteriorate. Further, the total content of Ce and B is preferably in the range of 4 to 15% by mass. When these additive elements are contained in a trace amount in the ZnO vapor deposition material, they do not exist as granular precipitates in the grain boundaries and grains of the ZnO matrix, but are uniformly dispersed in the ZnO vapor deposition material. . In the ZnO vapor deposition material, Ce is present as an oxide such as CeO ₂ or Ce ₂ O ₃ , and B is considered to be present as B ₂ O ₃ .

  The ZnO vapor deposition material which concerns on this invention consists of a pellet which has ZnO as a main component. This pellet is preferably 5 to 50 mm in diameter and 2 to 30 mm in thickness. The diameter of the pellets is set to 5 to 50 mm for the purpose of stable and high-speed film formation. If the diameter is less than 5 mm, there is a problem that splash or the like occurs. There is a defect that causes non-uniformity of the film in vapor deposition and a decrease in the film formation rate due to a decrease in filling rate. Further, the thickness is set to 2 to 30 mm for the purpose of stable and high-speed film formation. If the thickness is less than 2 mm, there is a problem that splash or the like occurs. There is a defect that causes non-uniformity of the film in vapor deposition and a decrease in the film formation rate due to a decrease in the filling rate into the reservoir. The ZnO pellets may be polycrystalline or single crystal.

  In the ZnO vapor deposition material of the present invention configured as described above, since trivalent or tetravalent rare earth element Ce is added as an additive element, by generating excess carrier electrons with respect to divalent Zn, High conductivity can be secured. Moreover, when rare earth is added to the ZnO vapor deposition material, it is a material that hardly causes a composition shift during vapor deposition, and a desired composition ratio can be maintained in the film. In addition to the forced injection of carrier electrons, the conduction mechanism includes oxygen vacancies. In general vapor deposition, oxygen gas is introduced, but in general, oxygen is insufficient in the film composition. Although a method of generating oxygen vacancies and reducing the resistance is employed in forming the transparent conductive film, when a rare earth element is added, there is a feature that it is easy to control because of its excellent evaporation performance. In the present invention, in addition to this feature, by including B as an additive element, a high conductivity approaching that of ITO can be obtained.

Next, the manufacturing method of a ZnO vapor deposition material is demonstrated on behalf of the case where it produces by a sintering method.
First, the high purity ZnO powder, the CeO ₂ powder in an amount such that the Ce content in the ZnO vapor deposition material is in the range of 3 to 14.9% by mass, and the B content in the ZnO vapor deposition material is 1 to 10 mass. % and the amount of B ₂ O ₃ powder in the range of, and a binder, by mixing the organic solvent, the concentration is 30 to 75 wt%, preferably to prepare a 40-65 wt% of the slurry. The high purity ZnO powder preferably has a purity of 98% or more, more preferably 98.4% or more. This is because if the purity of the ZnO powder is 98% or more, a decrease in conductivity due to the influence of impurities can be suppressed. The concentration of the slurry is limited to 30 to 75% by mass. If the slurry exceeds 75% by mass, the slurry is non-aqueous, so that stable mixing granulation is difficult, and if it is less than 30% by mass, a dense structure having a uniform structure is obtained. This is because it is difficult to obtain a ZnO sintered body. The average particle size of the ZnO powder is preferably in the range of 0.1 to 5.0 μm. If it is less than 0.1 μm, the powder is too fine and agglomerates, so that the handling of the powder tends to be poor, and it tends to be difficult to prepare a high-concentration slurry. This is because it tends to be difficult to obtain.

In consideration of prevention of uneven distribution of Ce abundance, reactivity with the ZnO matrix and purity of the Ce compound, CeO ₂ powder is preferably added with cerium oxide particles having a primary particle size of nanoscale. It is preferable to use a B ₂ O ₃ powder having an average particle diameter in the range of 0.01 to 1 μm. This is because the use of a powder having a diameter within the range of 0.01 to 1 μm is suitable for uniformly dispersing the B ₂ O ₃ powder. Among these, the thing of the range of 0.05-0.5 micrometer is especially preferable.

  It is preferable to use polyethylene glycol or polyvinyl butyral as the binder, and ethanol or propanol as the organic solvent. The binder is preferably added in an amount of 0.2 to 5.0% by mass.

The wet mixing of the high purity powder, the binder, and the organic solvent, particularly the wet mixing of the high purity powder and the organic solvent that is the dispersion medium is performed by a wet ball mill or a stirring mill. In the wet ball mill, when ZrO ₂ balls are used, wet mixing is performed for 8 to 24 hours, preferably 20 to 24 hours, using a large number of ZrO ₂ balls having a diameter of 5 to 10 mm. The reason why the diameter of the ZrO ₂ balls is limited to 5 to 10 mm is that mixing is insufficient when the diameter is less than 5 mm, and there is a problem that impurities increase when the diameter exceeds 10 mm. The reason why the mixing time is as long as 24 hours is that the generation of impurities is small even if the mixing is continued for a long time.

Next, the slurry is spray-dried to obtain a mixed granulated powder having an average particle size of 50 to 250 μm, preferably 50 to 200 μm. This granulated powder is put into a predetermined mold and molded at a predetermined pressure. The spray drying is preferably performed using a spray dryer, and the predetermined die is a uniaxial press device or a cold isostatic press (CIP (Cold Isostatic Press) molding device). In the uniaxial press apparatus, the granulated powder is uniaxially pressed at a pressure of 750 to 2000 kg / cm ² ( 73.55 to 196.1 MPa), preferably 1000 to 1500 kg / cm ² ( 98.1 to 147.1 MPa). In the CIP molding apparatus, the granulated powder is pressed at a pressure of 1000 to 3000 kg / cm ² ( 98.1 to 294.2 MPa), preferably 1500 to 2000 kg / cm ² ( 147.1 to 196.1 MPa). CIP molding. The reason why the pressure is limited to the above range is to increase the density of the molded body, prevent deformation after sintering, and eliminate the need for post-processing.

  Further, the molded body is sintered at a predetermined temperature. Sintering is carried out at a temperature of 1000 ° C. or higher, preferably 1200 to 1400 ° C. for 1 to 10 hours, preferably 2 to 5 hours in the atmosphere, inert gas, vacuum or reducing gas atmosphere. Thereby, the pellet which has desired ZnO as a main component is obtained. The relative density of the pellets is preferably 90% or more, and more preferably 95% or more. This is because if the relative density is 90% or more, splash during film formation can be reduced. The above sintering is performed under atmospheric pressure, but when performing pressure sintering such as hot pressing (HP) sintering or hot isostatic pressing (HIP) sintering, an inert gas, It is preferable to carry out at a temperature of 1000 ° C. or higher for 1 to 5 hours in a vacuum or a reducing gas atmosphere.

Next, a ZnO film is formed on the substrate surface by a vacuum film-forming method using the obtained polycrystalline ZnO vapor deposition material in pellets as a target material. Examples of the vacuum film formation method suitable for forming a film using the ZnO vapor deposition material of the present invention include an electron beam vapor deposition method, an ion plating method, a sputtering method, and a plasma vapor deposition method. Since the ZnO film of the present invention formed by these film forming methods uses the ZnO vapor deposition material of the present invention, the specific resistance approaching that of ITO is 3 to 5 × 10 ⁻⁴ Ω · cm. High conductivity and high transmittance with a visible light transmittance of 90% or more can be obtained. Furthermore, the durability of the film can be improved by adding a crystal having a ionic radius which is distorted by Ce larger than Zn and recovering and matching it by adding B having a small ionic radius.

The value of the average particle diameter of ZnO powder, B ₂ O ₃ powder and mixing the granulated powder used in the present invention is a value calculated or measured by a laser diffraction method.

Next, examples of the present invention will be described in detail together with comparative examples.
< Reference Example 1>
First, 994.28 g of ZnO powder, 2.50 g of CeO ₂ powder, 3.22 g of B ₂ O ₃ powder, a binder, and an organic solvent were wet mixed using a wet ball mill to prepare a slurry. The prepared slurry was spray-dried, and the obtained mixed granulated powder was press-molded at a pressure of 100.0 MPa, and then sintered at a temperature of 1300 ° C. to produce a ZnO vapor deposition material.

  The obtained ZnO vapor deposition material has a relative density of 95% and, as shown in Table 1 below, a polycrystalline ZnO pellet having a Ce concentration of 0.2% by mass and a B concentration of 0.1% by mass. Met. The diameter and thickness of the pellets were 5 mm and 1.6 mm, respectively.

Next, a 200 nm-thick ZnO film was formed on a glass substrate (non-alkali glass) by the electron beam evaporation method using the ZnO evaporation material. Specifically, the ultimate vacuum degree is 2.66 × 10 ⁻⁴ Pa and the partial pressure of oxygen is 1.33 × 10 ⁻² on the ZnO vapor deposition material charged in the hearth of the electron beam vapor deposition apparatus having a diameter of 50 mm and a depth of 25 mm. In this atmosphere, an electron beam having an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ was irradiated and heated.

<Example 1 >
A ZnO vapor deposition material was prepared in the same manner as in Reference Example 1 except that 930.9 g of ZnO powder, 36.9 g of CeO ₂ powder and 32.2 g of B ₂ O ₃ powder were used, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 3% by mass and the B concentration was 1% by mass.

<Example 2 >
A ZnO vapor deposition material was prepared in the same manner as in Reference Example 1, except that the ZnO powder was 829.7 g, the CeO ₂ powder was 73.7 g, and the B ₂ O ₃ powder was 96.6 g, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 6% by mass and the B concentration was 3% by mass.

<Example 3 >
A ZnO vapor deposition material was prepared in the same manner as in Reference Example 1, except that the ZnO powder was 494.98 g, the CeO ₂ powder was 183.00 g, and the B ₂ O ₃ powder was 322.02 g, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 14.9% by mass and the B concentration was 10% by mass.

<Comparative Example 1>
A ZnO vapor deposition material was prepared in the same manner as in Reference Example 1 except that 999.43 g of ZnO powder, 0.25 g of CeO ₂ powder, and 0.32 g of B ₂ O ₃ powder were used, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 0.02 mass% and the B concentration was 0.01 mass%.

<Comparative example 2>
A ZnO vapor deposition material was prepared in the same manner as in Reference Example 1 except that the ZnO powder was 754.3 g, the CeO ₂ powder was 245.7 g, and the B ₂ O ₃ powder was not added, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95% and, as shown in Table 1 below, the Ce concentration was 20% by mass. That is, the obtained ZnO vapor deposition material does not contain B.

<Comparative Example 3>
A ZnO vapor deposition material was prepared in the same manner as in Reference Example 1 except that 271.28 g of ZnO powder, 245.70 g of CeO ₂ powder, and 483.02 g of B ₂ O ₃ powder were used, and a ZnO film was formed on the glass substrate. Was deposited. In addition, the obtained ZnO vapor deposition material had a relative density of 95%, and as shown in Table 1 below, the Ce concentration was 20 mass% and the B concentration was 15 mass%.

<Comparative example 4>
A ZnO vapor deposition material was prepared in the same manner as in Reference Example 1 except that the ZnO powder was 516.98 g, the B ₂ O ₃ powder was 483.02 g, and the CeO ₂ powder was not added, and a ZnO film was formed on the glass substrate. Was deposited. The obtained ZnO vapor deposition material had a relative density of 95% and a B concentration of 15% by mass as shown in Table 1 below. That is, the obtained ZnO vapor deposition material does not contain Ce.

<Comparative Example 5>
A ZnO vapor deposition material was prepared and a ZnO film was formed on a glass substrate in the same manner as in Reference Example 1 except that the ZnO powder was 1000 g and the B ₂ O ₃ powder and CeO ₂ powder were not added. In addition, the obtained ZnO vapor deposition material was a ZnO vapor deposition material which has a relative density of 95% and does not contain Ce and B.

<Comparison test and evaluation>
For the ZnO films formed in Reference Example 1 , Examples 1 to 3 and Comparative Examples 1 to 5, specific resistance and transmittance were measured. The results are shown in Table 1 below. The specific resistance was measured by a four-terminal four-probe method by applying a constant current at 25 ° C. using a measuring instrument (Mitsubishi Chemical Corporation, trade name: Loresta HP type, MCP-T410, probe: series 1.5 mm pitch). . The transmittance was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.) in the visible light wavelength range (380 to 780 mm) by placing the substrate after film formation perpendicular to the measurement light.

As it is evident from Table 1, Reference Example 1, comparing the Comparative Examples 1-5 and Examples 1 3 and Comparative Examples 1-5, Reference Example 1, Examples 1 3 and Comparative Examples 1 to 5 ZnO The specific resistance of the film was lower than those of Comparative Examples 1-5. With respect to the transmittance, ZnO films of Examples 1 to 3, although was slightly lower than Comparative Example 1 and 5, in comparison with Comparative Example 2-4, it can be said that a sufficiently high transmittance is obtained. From this, it was confirmed that the ZnO vapor deposition material of the present invention is effective.

Claims (6)

In a ZnO vapor deposition material used for forming a transparent conductive film,
Consisting of pellets based on ZnO,
The pellet contains both elements of Ce and B;
The Ce content is higher than the B,
The ZnO vapor deposition material, wherein the Ce content is 3 to 14.9% by mass, and the B content is 1 to 10% by mass. The ZnO vapor deposition material according to claim 1, wherein the total content of Ce and B is in the range of 4 to 15 mass%.   The ZnO vapor deposition material according to claim 1, wherein the ZnO pellet is a polycrystal or a single crystal. A method for producing a ZnO vapor deposition material according to any one of claims 1 to 3,
CeO in which the content ratio of Ce in the ZnO powder and the ZnO vapor deposition material is in the range of 3 to 14.9% by mass. ₂ B in which the content of B in the powder and ZnO vapor deposition material is in the range of 1 to 10% by mass ₂ O _Three A powder, a binder, and an organic solvent are mixed to prepare a slurry having a concentration of 30 to 75% by mass, and the Ce content ratio in the ZnO vapor deposition material is higher than the B content ratio,
  The slurry is spray-dried to produce a mixed granulated powder having an average particle size of 50 to 250 μm,
  The mixed granulated powder is put in a predetermined mold and molded at a predetermined pressure,
  The manufacturing method of the ZnO vapor deposition material which obtains the ZnO vapor deposition material which consists of a pellet by sintering the molded object obtained by the said shaping | molding at the temperature of 1000 degreeC or more for 1 to 10 hours. A ZnO film formed by a vacuum film forming method using the ZnO vapor deposition material according to any one of claims 1 to 3 or the ZnO vapor deposition material obtained by the manufacturing method according to claim 4 as a target material. 6. The ZnO film according to claim 5, wherein the vacuum film forming method is an electron beam vapor deposition method, an ion plating method, a sputtering method or a plasma vapor deposition method.