JP6772473B2 - Gallium nitride based sintered body and its manufacturing method - Google Patents

Description

Gallium nitride has attracted attention as a light emitting layer for blue light emitting diodes (LEDs) and as a raw material for blue laser diodes (LDs), and in recent years it has been used in various applications such as white LEDs and blue LDs in the form of thin films and substrates. In the future, it is also attracting attention as a material for applications such as power devices. Currently, gallium nitride thin films are generally manufactured by the metalorganic chemical vapor deposition (MOCVD) method. The MOCVD method is a method in which crystals are grown by impregnating carrier gas with vapor of a raw material, transporting the raw material to the surface of the substrate, and decomposing the raw material by reaction with a heated substrate.

As a method for producing a thin film other than the MOCVD method, a sputtering method can be mentioned. In this sputtering method, positive ions such as Ar ions are physically collided with a target installed on a cathode, and the material constituting the target is released by the collision energy, and the composition is almost the same as that of the target material on a substrate installed facing each other. There are a DC sputtering method (DC sputtering method) and a high frequency sputtering method (RF sputtering method).

So far, a metal gallium target has been used as a method for forming a gallium nitride thin film by a sputtering method (see, for example, Patent Document 1). However, when a metallic gallium target is used, since the melting point of metallic gallium is about 29.8 ° C., it dissolves during sputtering, so that a gallium nitride film having highly stabilized characteristics such as crystallinity and permeability can be obtained. It is difficult to do so, and in order to prevent it, a method of installing an expensive cooling device and forming a film with low power has been proposed, but the productivity decreases and the uptake of oxygen into the film also increases. There was a problem that it was easy.

A high-density gallium nitride sintered body has also been proposed (see, for example, Patent Document 2), but according to this embodiment, it is densified under a very high pressure condition of 58 Kbar (5.8 GPa). A device that applies a large amount of pressure is a very expensive device, and a large sintered body cannot be produced. Therefore, the sputtering target itself used in the sputtering method is very expensive, and it is difficult to increase the size, so that there is a problem that the film tends to be inferior in homogeneity.

Further, as a method for reducing the amount of oxygen contained, a method for reducing the amount of oxygen by nitriding a gallium nitride sintered body containing oxygen has been proposed (see, for example, Patent Document 3). However, there is a problem that cracks may occur in the sintered body when the amount of oxygen is reduced above a certain level.

Further, when the DC sputtering method is used, the resistivity of the sputtering target is required to be low. As a method for this, a method of reducing the resistivity of a sputtering target by impregnating a gallium nitride molded product with metallic gallium has been proposed (see, for example, Patent Document 4). However, in this method, although the resistance is reduced, there is a problem that metallic gallium precipitates during bonding or sputtering, which reacts with a solder material such as indium and exfoliates the gallium nitride molded product, so that discharge cannot be performed stably. there were. As a countermeasure, a method of suppressing the precipitation of metallic gallium by lining a thin film of tungsten has been proposed (see, for example, Patent Document 5), but the number of target preparation steps increases, which makes it complicated and expensive. There was a problem that it was necessary to use a special material called a tungsten material.

JP-A-11-172424 Japanese Unexamined Patent Publication No. 2005-508822 Japanese Unexamined Patent Publication No. 2012-144424 Japanese Unexamined Patent Publication No. 2014-159368 Japanese Unexamined Patent Publication No. 2014-91851

An object of the present invention is to provide a gallium nitride based sintered body having a low oxygen content, a high density and a low resistance, and in which metal gallium is less likely to precipitate, and a method for producing the same.

In view of such a background, the present inventors have made extensive studies. As a result, gallium nitride powder, which has low oxygen content and high bulk density, is used and hot-pressed at high temperature under high vacuum to achieve high-density, low-resistance sintering with low oxygen content. We have found that a gallium nitride-based sintered body can be produced and a conductive gallium nitride-based sputtering target can be produced without performing a backing treatment using a special material, and the present invention has been completed.

That is, the aspects of the present invention are as follows.
(1) A gallium nitride-based sintered body having an oxygen content of 1 atm% or less and a resistivity of 1 × 10 ² Ω · cm or less.
(2) The sintered body according to (1), wherein the density is 3.0 g / cm ³ or more and 5.4 g / cm ³ or less.
(3) The sintered body according to (1) or (2), wherein the average particle size of the sintered body is 0.5 μm or more and 3 μm or less.
(4) The sintered body according to any one of (1) to (3), wherein the weight of the sintered body is 10 g or more.
(5) The sintered body according to any one of (1) to (4), wherein precipitation of metallic gallium cannot be visually confirmed from the target member even after heat treatment at 250 ° C. for 1 hour in the atmosphere. ..
(6) A method for producing a gallium nitride-based sintered body by a hot press method, in which gallium nitride powder having an oxygen content of 2 atm% or less is used as a raw material, and the ultimate vacuum degree in the chamber during hot pressing is 70 Pa or less and 1060 ° C or more. A method for producing a gallium nitride-based sintered body, which comprises heating at a temperature lower than 1300 ° C.
(7) A gallium nitride sputtering target characterized by using the sintered body according to any one of (1) to (5).
(8) The sputtering target according to (7), wherein there is no layer containing tungsten between the target member and the bonding layer.
(9) The sputtering target according to (7) or (8), wherein the bonding layer contains at least one component of indium, tin, and zinc.
(10) A method for producing a gallium nitride-based thin film, which comprises using the sputtering targets according to (6) to (9).

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments.

The gallium nitride sintered body of the present invention is characterized by having an oxygen content of 1 atm% or less, preferably 0.5 atm% or less. By reducing the oxygen content in the sintered body, when it is used as a sputtering target, it is possible to reduce the mixing of oxygen as an impurity during film formation and obtain a film having higher crystallinity.

Further, gallium nitride sintered body of the present invention, the resistivity, characterized in that at 1 × 10 ² Ωcm or less, more preferably ¹ × 10 1 Ωcm or less, more preferably 1 × 10 ⁰ Ωcm or less .. When the low resistance sintered body is used as a sputtering target, not only RF sputtering but also DC sputtering can be performed.

The gallium nitride sintered body of the present invention preferably has a density of 3.0 g / cm ³ or more and 5.4 g / cm ³ or less, and the lower limit thereof is more preferably 3.5 g / cm ³ or 4.0 g / cm. ³ is more preferable. The density of the gallium nitride sintered body described here refers to the density including the open pores, and refers to the measurement result of the bulk density in JISR1634. Such a gallium nitride based sintered body can be used as a sputtering target.

The gallium nitride sintered body of the present invention preferably has an average particle size of 0.5 μm or more and 3 μm or less. By setting such a particle size, it is possible to obtain a sintered body having few open pores, a low oxygen content, and high strength.

Next, a method for producing the gallium nitride sintered body will be described.

As a result of detailed examination of the relationship between the specific surface area (BET) of the gallium nitride powder as a raw material, the light bulk density, and the particle size of the primary particles and the strength of the sintered body, the above-mentioned physical property values of the gallium nitride powder should be controlled. It was found that it is possible to reduce the mixing of impurities with oxygen and to obtain a sintered body having high strength.

That is, the production method of the present invention is a method for producing a gallium nitride based sintered body by a hot press method, in which gallium nitride powder having an oxygen content of 2 atm% or less is used as a raw material, and the ultimate vacuum degree in the chamber during hot pressing is high. It is characterized by heating at 70 Pa or less, 1060 ° C. or higher and lower than 1300 ° C. With such a manufacturing method, even a gallium nitride based sintered body having a weight of 10 g or more can be manufactured with a high yield.

The manufacturing method will be described in more detail below.

First, the gallium nitride powder used as a raw material needs to have an oxygen content of 2 atm% or less. In order to reduce oxygen, it is necessary to suppress surface oxidation, so the specific surface area of the powder is preferably small, preferably 1.5 m ² / g or less, and more preferably 0.8 m ^2. It is less than / g. By using such a powder, it is possible to reduce the amount of oxygen mixed in the powder. The lower limit is preferably larger than 0.1 m ² / g. If the specific surface area is smaller than that, the crystal particles are too large, and the adhesive force between the particles is weak, making it difficult to retain the shape during final firing. Furthermore, if the specific surface area is small, Generally, the sinterability is lowered, which makes firing difficult.

Further, in order to obtain a sintered body having sufficient strength as a sputtering target, the light bulk density of gallium nitride as a raw material is preferably 0.8 g / cm ³ or more, more preferably 1.0 g / cm. ³ or more. The light bulk density is a value obtained by filling a container having a certain volume with powder without applying a load such as vibration and dividing the volume of the filled powder by the volume of the container. The light bulk density is preferably less than 2.5 g / cm ³ . If the light bulk density is increased more than that, the strength of the granules constituting the powder becomes too high, and the granules remain without being crushed during molding and firing, so that the strength of the sintered body is significantly reduced.

The average particle size of gallium nitride used as a raw material is preferably 0.5 μm or more and 3 μm or less. By using such a powder, it becomes possible to produce a sintered body having both sinterability and low oxygen content. Especially in gallium nitride, the sintering start temperature and the decomposition temperature are close to each other, the sintering temperature range is narrow, and the particles do not grow large during sintering. Therefore, the distribution of primary particles before sintering has a great influence on the sintered body. give. The particle size of the primary particles refers to the diameter of the smallest unit of particles observed by SEM, and the average particle size is measured by the diameter method, measured for at least 100 or more particles, and then a numerical value at 50% particle size. Point to. In the case of a molded product using powder in this range, the particle size is larger and the adhesive force is smaller than before, so if there are open pores to the extent that it can be immersed, the bonding force between the particles is relatively weak. When dipping is performed, cracks occur due to the stress generated during dipping and the difference in thermal expansion coefficient caused by heating and sputtering.

Since the semiconductor characteristics change due to the high crystallinity of the sputtering film and the addition of elements, it is desirable to use gallium nitride powder as a raw material that does not contain impurities as much as possible.

A hot press method is used as the firing method. The hot press method is a method in which sintering is promoted by applying temperature while pressurizing the powder. Uniaxial pressurization during heating assists diffusion during firing, and a material with a low diffusion coefficient and difficult to sinter is used. This is a firing method that enables sintering.

The firing temperature is 1060 ° C or higher and lower than 1300 ° C. 1060 ° C or higher is required to proceed with the sintering of gallium nitride, and it must be lower than 1300 ° C to suppress the decomposition of gallium nitride into nitrogen and metallic gallium to a certain amount. Further, in order to improve the density of the sintered body, the pressure at the time of firing is preferably 30 MPa or more and 100 MPa or less, and more preferably 50 MPa or more and 90 MPa or less.

The atmosphere in the hot press is under vacuum. Not more than the degree of vacuum 70Pa at the start of heating is preferably 10Pa or ^less, more preferably ¹⁰ -1 ^Pa, and particularly preferably ¹⁰ -2 Pa or less. This makes it possible to reduce oxygen and oxygen elements such as water mixed in from the atmosphere and suppress oxidation during firing.

Further, when sintering under vacuum, the decomposition of gallium nitride powder gradually proceeds from around 1060 ° C., but by sintering under vacuum, a part of the metal gallium generated by decomposition is combined with nitrogen which is a decomposition gas. It is discharged from the sintered body to the outside. Therefore, in the hot press type, it is preferable that the clearance between the die and the upper punch is 0.2 mm or more. Alternatively, it is preferable to use a material having a low density such as carbon felt between the powder and the upper and lower punches.

When the hot press treatment is performed under the above-mentioned conditions, metallic gallium does not act as an inhibitor during sintering and contains an appropriate amount. Therefore, as the sintering progresses, the density is high and oxidation is suppressed. It is possible to obtain a gallium nitride sintered body. In particular, in the region of 1060 ° C. or higher and 1300 ° C. or lower, metallic gallium is partially decomposed, but since gallium nitride sintering also progresses, it is hindered by metallic gallium by performing pressure sintering with high vacuum. The density is improved by the progress of sintering of gallium nitride. When gallium nitride is used as a sputtering target, it is preferable that the sintered body has conductivity, and for that purpose, metallic gallium is preferably present. Whether or not metallic gallium is contained in gallium nitride is clear by checking the resistivity of the sintered body, and the substrate has a high resistivity as represented by the gallium nitride single crystal, but as in the present invention. a sintered body resistivity is as low as less than 10 ² Ω · cm. Molds and sintered bodies in which the decomposition of gallium nitride has not progressed even when the same raw material is used have high resistivity. Various methods of containing metallic gallium in the gallium nitride sintered body can be considered, but in order to uniformly and in a small amount, the method of dispersing the metallic gallium in the gallium nitride raw material powder or the method of decomposing the gallium nitride during sintering Therefore, a method for producing gallium nitride is preferable. By doing so, it becomes possible to uniformly disperse a small amount of metallic gallium in the sintered body. Its content is preferably less than 30 wt%, more preferably less than 10 wt%.

The obtained sintered body may be processed to a predetermined size depending on the application such as a sputtering target. The processing method is not particularly limited, but a surface grinding method, a rotary grinding method, a cylindrical grinding method, or the like can be used.

The gallium nitride sintered body may be fixed (bonded) to a flat plate-shaped or cylindrical support with an adhesive such as a solder material, if necessary, and may be used as a sputtering target. The sputtering target preferably has no layer containing tungsten between the target member and the bonding layer. By not using an expensive metallic tungsten target, the cost is reduced and the tungsten film forming process is not required, so that the productivity is improved.

Further, as the sputtering target of the present invention, it is preferable to use a tin-based solder material, an indium-based solder material, or a zinc-based solder material as the bonding layer. Among them, indium solder having high conductivity and thermal conductivity, and being soft and easily deformed is particularly preferable.

Further, the sputtering target of the present invention is preferably a metal such as Cu, SUS or Ti because it has high thermal conductivity and high strength as a support. As for the shape of the support, it is preferable to use a flat plate-shaped support for the flat plate-shaped molded product and a cylindrical support for the cylindrical molded product.

Next, the method for manufacturing the sputtering target of the present invention will be described.

The gallium nitride sintered body is bonded to the support via a bonding layer. A tin-based solder material, an indium-based solder material, a zinc-based solder material, or the like can be used for the bonding layer, but when an indium-based solder material is used, the indium wettability to the gallium nitride sintered body is improved. In order to improve, a layer for improving wettability may be formed between the sintered body and the solder material. The material of the layer is preferably inexpensive and has high wettability to indium, and for example, nickel-based or chromium-based is preferable. It is preferable that this layer is uniformly formed over the entire interface with the solder material. The method for forming such a barrier layer is not particularly limited, but sputtering, vapor deposition, coating, or the like is used.

The gallium nitride sintered body of the present invention has a low oxygen content, high density, and low resistance, and metal gallium is less likely to precipitate, so that it is suitable for use as a sputtering target.

Hereinafter, description will be given with reference to examples, but the present invention is not limited thereto.
(Specific surface area)
The specific surface area of the powder was measured using a Micrometrics Tristar.
(Light bulk density)
The measurement was performed using a powder tester PT-N type (manufactured by Hosokawa Micron).
(Bulk density of sintered body)
The bulk density of the sintered body was measured according to the method of bulk density measurement in JISR1634.
(Oxygen content)
The oxygen content of the sintered body was measured by an oxygen / nitrogen analyzer (manufactured by LECO).
(Heating test)
The sintered body was heat-treated at 250 ° C. for 1 hour using a hot plate in the atmosphere, and the presence or absence of precipitation of metallic gallium from the sintered body was visually confirmed.
(Measurement of particle size)
The particle size of the powder and the sintered body was measured from the observation image by SEM by the diameter method for at least two visual fields, and after measuring 100 or more particles, the 50% particle size was taken as the average particle size.
(Confirmation of crystal plane, measurement method of half-value width and strength ratio)
A general powder X-ray diffractometer (device name: UltraIII, manufactured by Rigaku Co., Ltd.) was used for normal measurement. The conditions for XRD measurement are as follows.
Source: CuKα ray (λ = 0.15418 nm)
Measurement mode: 2θ / θ scan
Measurement interval: 0.01 °
Divergence slit: 0.5 deg
Scattering slit: 0.5 deg
Light receiving slit: 0.3 mm
Measurement time: 1.0 second
Measurement range: 2θ = 20 ° to 80 °
XRD analysis software (trade name: JADE7, manufactured by MID) was used for the identification analysis of the XRD pattern. Hexagonal crystals are JCPDS No. Check the gallium nitride crystal plane with reference to 00-050-0792, measure the half-value width of the (002) plane, and calculate the intensity ratio for I (002) and I (101) using the following formula. ..
Intensity ratio = I (002) / I (101)
If the peak that seems to be the (101) plane is not detected, the background peak intensity of 36 to 37 ° is regarded as I (101) and the calculation is performed.

High-precision measurement was performed with the following configuration of an XRD device (D8 DISCOVER manufactured by Bruker), and CuKα2 was removed using a HIGH RESULTION mode and a Ge (220) monochromator under the conditions of 40 kV and 40 mA, and an ω scan was performed. ..
Source: CuKα ray (λ = 0.15418 nm)
Monochromator: Ge (220)
Pathfinder: Crystal3B
Measurement mode: ω scan
Measurement interval: 0.01 °
(0.0005 ° when the half price range is 0.1 ° or less)
Measurement time: 0.5 seconds
Measurement range: ω = 0 ° to 35 °
(Measurement of oxygen content in the membrane)
The oxygen content in the membrane was measured using SIMS (Secondary Ion Mass Spectrometer). The oxygen content was measured in the depth direction of the film, and the minimum content between 5 nm and 30 nm was calculated from the interface with respect to the place assumed to be the substrate.

(Examples 1 to 4)
Using 30 g of the gallium nitride powder shown in Table 1, the gallium nitride powder was charged into a 51 mmφ carbon die and charged into a hot press. As for the ultimate vacuum degree before the start of temperature rise, firing is started under the conditions shown in Table 1, the temperature is raised at 200 ° C./h, and finally the temperature is increased to the temperature shown in Table 1, and the temperature is increased at that time. The pressure condition was raised to the pressure shown in Table 1 when the maximum temperature was maintained, and the hot press treatment was performed with the temperature and pressure holding time of 1 hour. The temperature was lowered to about 50 ° C. in 5 hours, the mold was taken out, and the sintered body was recovered. All were sintered bodies of 10 g or more. Table 2 shows the weight, density, oxygen content, resistivity, average particle size, and heating test results of the obtained polycrystalline gallium nitride sintered body.

After further processing the sintered body and bonding it to the backing plate, it was confirmed whether or not it was possible to form a film by DC or RF as a sputtering target. All the samples were bonded without any problem, and DC / RF was used. It was confirmed that film formation was possible.

(Example 5)
250 g of the gallium nitride powder shown in Table 1 was put into a 130 mmφ carbon mold and put into a hot press. As for the ultimate vacuum degree before the start of temperature rise, firing is started under the conditions shown in Table 1, the temperature is raised at 200 ° C./h, and finally the temperature is increased to the temperature shown in Table 1, and the temperature is increased at that time. The pressure condition was raised to the pressure shown in Table 1 when the maximum temperature was maintained, and the hot press treatment was performed with the temperature and pressure holding time of 2 hours. After the temperature was lowered, the mold was taken out and the sintered body was recovered. Table 2 shows the weight, density, oxygen content, resistivity, average particle size, and heating test results of the obtained polycrystalline gallium nitride sintered body.

(Comparative Examples 1 to 3)
Using the gallium nitride powder shown in Table 1, hot pressing was performed under the same heating rate, holding time, and lowering conditions as in Example 1 except that the degree of vacuum, firing temperature, and load in Table 1 were set. Table 2 shows the weight, density, oxygen content, resistivity, average particle size, and heating test results of the polycrystalline gallium nitride sintered body. In Comparative Example 2, the shape could not be maintained and a sintered body could not be obtained.

(Comparative Example 4)
Metal gallium (purity 6N, oxygen content 0.0174 atm%, DOWA Electronics Co., Ltd.) with respect to 24.5 g of the processed gallium nitride sintered body with respect to the gallium nitride sintered body produced under the same conditions as in Comparative Example 1. (Manufactured by the company) was prepared in an amount 1.35 times that of the sintered body, and both were put into a vacuum packaging bag and vacuum packaged at 1000 Pa. The packaging container was heated to about 50 ° C. to completely dissolve the metallic gallium, and then the container was charged into CIP and pressurized at 100 MPa for 60 seconds. After taking out and heating at about 50 ° C., the metal gallium remaining in the periphery was removed to obtain a metal gallium osmotic gallium nitride sintered body. On the other hand, when a heating test was carried out at 250 ° C., precipitation of Ga metal was observed. The values of the average particle size shown in Table 2 relate to the average particle size of the sintered body before the metal gallium is infiltrated, and the weight, density, oxygen content, resistance and the result of the heating test are shown. It relates to a metal gallium penetrating gallium nitride sintered body.

(Reference example)
An attempt was made to prepare a metallic gallium penetrant by the same method as in Comparative Example 4 with respect to the sintered body prepared by the same method as in Example 1, but cracks occurred during permeation.

実施例５と比較例１について下記の条件にて成膜を実施したところ、本発明により膜中の酸素量、膜の結晶性、配向性が大きく改善することを確認した。
（スパッタ成膜条件）
ターゲットサイズ：１２０ｍｍφ
放電電力 ：１２５Ｗ
スパッタガス圧 ：０．０７Ｐａ
スパッタガス ：窒素のみ
成膜温度 ：６００℃
膜厚 ：約３００ｎｍ

When film formation was carried out for Example 5 and Comparative Example 1 under the following conditions, it was confirmed that the amount of oxygen in the film, the crystallinity of the film, and the orientation were greatly improved by the present invention.
(Sputter film formation conditions)
Target size: 120mmφ
Discharge power: 125W
Sputter gas pressure: 0.07 Pa
Sputter gas: Nitrogen only Film formation temperature: 600 ° C
Film thickness: Approximately 300 nm

Claims (4)

The gallium nitride sintered body is sputtered even if the oxygen content by the hot press method is 1 atm% or less, the resistance is 1 × 10 ² Ω · cm or less, and the heat treatment at 250 ° C. is performed in the air for 1 hour. This is a method for manufacturing a gallium nitride sintered body in which the precipitation of metallic gallium cannot be visually confirmed from the targeted target member. The gallium nitride powder having an oxygen content of 2 atm% or less is used as a raw material, and the ultimate vacuum in the chamber during hot pressing. A method for producing a gallium nitride sintered body, which comprises heating at a degree of 70 Pa or less and 1060 ° C or more and less than 1300 ° C. The method for producing a gallium nitride sintered body according to claim 1, wherein the density is 3.0 g / cm ³ or more and 5.4 g / cm ³ or less. The method for producing a gallium nitride sintered body according to claim 1 or 2, wherein the average particle size of the sintered body is 0.5 μm or more and 3 μm or less. The method for producing a gallium nitride sintered body according to any one of claims 1 to 3, wherein the weight of the sintered body is 10 g or more.